Composition for forming resist underlayer film

Abstract

This composition for forming a resist underlayer film contains a polymer (A), a compound (B) having polymerizable multiple bonds, and a solvent (C).

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, not intermixing with a resist film formed on top (being insoluble in a resist solvent), being able to form a good resist pattern by improving the sensitivity and adhesion of the resist pattern, etc. 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 can improve the sensitivity and adhesion to form a good 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 encompasses the following aspects. [1] A composition for forming a resist underlayer film, comprising a polymer (A), a compound (B) having a polymerizable multiple bond, and a solvent (C). [2] The composition for forming a resist underlayer film according to [1], wherein the compound (B) is a reaction product of a reactant comprising a compound (B-1) having an epoxy group and a compound (B-2) having a polymerizable multiple bond and capable of reacting with an epoxy group. [3] The composition for forming a resist underlayer film according to [1], wherein the compound (B) is a reaction product of a reactant comprising a compound (B-3) having a hydroxy group and a compound (B-4) having a polymerizable multiple bond and capable of reacting with a hydroxy group. [4] The composition for forming a resist underlayer film according to any of [1] to [3], wherein the content of the polymer (A) is greater than the content of the compound (B). [5] The composition for forming a resist underlayer film according to any of [1] to [4], wherein the solvent (C) comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers. [6] The composition for forming a resist underlayer film according to any one of [1] to [5], further comprising a crosslinking agent (D). [7] The composition for forming a resist underlayer film according to [6], wherein the crosslinking agent (D) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. [8] The composition for forming a resist underlayer film according to any one of [1] to [7], further comprising a curing catalyst (E). [9] The composition for forming a resist underlayer film according to any one of [1] to [8], which is used for EUV lithography.

[10] The composition for forming a resist underlayer film according to any one of [1] to [9], which is used for forming an underlayer film of a metal-containing resist.

[11] 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

[10] .

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

[11] .

[13] 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

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

[14] A pattern forming method 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

[10] ; 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 can improve sensitivity and adhesion to form a good 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), a compound (B), and a solvent (C). The composition for forming a resist underlayer film may also contain a crosslinking agent (D), a curing catalyst (E), and the like. The compound (B) has a polymerizable multiple bond. The polymer (A) is, for example, different from the compound (B). By further adding the compound (B) having a polymerizable multiple bond to the composition for forming a resist underlayer film containing the polymer (A) and the solvent (C), a good resist pattern with improved sensitivity and adhesion can be formed on the resist underlayer film formed from the composition for forming a resist underlayer film.

[0010] <Polymer (A)> The polymer (A) is not particularly limited. Examples of the polymer (A) include polymers used in compositions for forming resist underlayer films. Polymers (A1) to (A12), which are examples of the polymer (A), are described below.

[0011] <<Polymer (A1)>> The polymer (A1) is a polymer having, in its main chain, at least one ring structure which is a heterocycle. Such a polymer is preferably a polymer (Y) having a repeating unit represented by the following formula (Y): (In formula (Y), A １ , A ２ , A３ , A ４ , A ５ , and A ６ represents a hydrogen atom, a methyl group, or an ethyl group. １ represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0); Q represents the following formula (Y5) or the following formula (Y6).

[0012] (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, 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 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, 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, a benzyl group, or a phenyl 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, 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 bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom.

[0013] (In formula (Y5) and formula (Y6), Q １represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, 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 X represents 0 or 1. ２ represents the formula (Y2), the formula (Y3), the formula (Y4), or the formula (Y0). * represents a bond.

[0014] Examples of the repeating unit represented by formula (Y) include repeating units represented by the following formulae (Y-1) to (Y-20).

[0015] In formula (Y-20), R is an alcohol residue (an organic group other than the hydroxy group of an alcohol), and this R represents an alkyl group, an ether group, or a combination thereof. Examples of R include an alkyl group and an alkoxyalkyl group.

[0016] Examples of polymer (Y) include polymers described in WO 2013 / 018802, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0017] The polymer (Y) is preferably produced by reacting a compound represented by the following formula (Y7) with a compound represented by the following formula (Y8). (In formula (Y7), X １ represents the formula (Y2), the formula (Y3), the formula (Y4), or the formula (Y0). In formula (8), Q represents the formula (Y5) or the formula (Y6). １ , A２ , A ３ , A ４ , A ５ , and A ６ each represents a hydrogen atom, a methyl group, or an ethyl group.

[0018] 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.

[0019] 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.

[0020] The weight average molecular weight of the polymer (A1) 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.

[0021] <<Polymer (A2)>> The polymer (A2) is a polymer obtained by polymerizing the polymerizable unsaturated bond of a compound having a group having a polymerizable unsaturated bond. The polymer (A2) may be a homopolymer or a copolymer. Examples of the group having a polymerizable unsaturated bond include a (meth)acryloyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, and an allyl group.

[0022] The polymer (A2) has, for example, at least one of a structural unit represented by the following formula (Z2), a structural unit represented by the following formula (Z3), and a structural unit represented by the following formula (Z4). (In formula (Z2), R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; L ３ represents a monovalent group having 1 to 20 carbon atoms. ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Ar represents a benzene ring or a naphthalene ring, L ４ is a hydroxy group, a cyano group, a nitro group, or an amino group (-NH ２ ) represents. ５ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. m1 represents an integer of 0 to 3. m2 represents an integer of 0 to 5, provided that the sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L ４ may be the same or different. When m2 is 2 to 5, multiple L ５ may be the same or different. ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; L ６ represents a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.

[0023] L in formula (Z2) ３ The monovalent group having 1 to 20 carbon atoms represents, for example, a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group. In addition, the alkyl group may have an oxygen atom inserted between carbon atoms. In addition, L ３ Examples of the monovalent group having 1 to 20 carbon atoms include groups represented by the following formula (Z2-1). (In formula (Z2-1), L ３ａ represents an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted aromatic hydrocarbon group. ３ａ Examples of the aromatic hydrocarbon group in L include a phenyl group and a naphthyl group. ３ａ Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom and a hydroxy group. The number of substituents may be one or more. When there are more than one substituent, the multiple substituents may be the same or different. ３ａ Examples of the substituent in the optionally substituted aromatic hydrocarbon group include a halogen atom, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom. The number of substituents may be one or more. When there are multiple substituents, the multiple substituents may be the same or different.

[0024] R ２ an alkyl group having 1 to 10 carbon atoms represented by the formula: ３ and L ６ Specific examples of the alkyl group having 1 to 10 carbon atoms represented by are as described above. ５ Examples of the halogen atom in L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ５ Examples of the alkyl group having 1 to 6 carbon atoms in the formula (L) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, and an i-butyl group. ５ Examples of the alkoxy group having 1 to 6 carbon atoms in the formula (I) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. m1 represents an integer of 0 to 3 and may be 0, 1, 2, or 3. m2 represents an integer of 0 to 5 and may be 0, 1, 2, 3, 4, or 5.

[0025] L ３ and L ６Examples of the aryl group having 6 to 40 carbon atoms represented by L include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. ６ Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0026] Examples of the monomers used to derive formula (Z2) include the following compounds:

[0027] Examples of the monomers used to derive formula (Z3) include the following compounds: Me represents a methyl group.

[0028] Examples of the monomers used to derive formula (Z4) include the following compounds:

[0029] The proportion of the structural unit represented by formula (Z2) in the polymer (A2) is not particularly limited, but the molar ratio of the structural unit represented by formula (Z2) relative to all structural units of the polymer (A2) may be, for example, 20 mol % to 100 mol %, or may be 20 mol % or more but less than 100 mol %.

[0030] The polymer (A2) may contain structural units other than the structural units represented by formula (Z2). In such cases, the molar ratio of the other structural units to all structural units of the polymer (A2) is, for example, more than 0 mol % and not more than 20 mol %.

[0031] Examples of polymer (A2) include polymers described in WO 2015 / 178235, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0032] The molecular weight of the polymer (A2) is not particularly limited. The lower limit of the weight average molecular weight of the polymer (A2) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight average molecular weight of the polymer (A2) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0033] <<Polymer (A3)>> The polymer (A3) has a polycyclic aromatic hydrocarbon structure in a side chain. Hereinafter, the unit structure (C1) having a polycyclic aromatic hydrocarbon structure contained in the polymer (A3) will be described.

[0034] <<<<Unit Structure (C1)>>> As described above, the unit structure (C1) is a unit structure having a polycyclic aromatic hydrocarbon structure. The polycyclic aromatic hydrocarbon structure preferably includes at least one structure selected from the group consisting of naphthalene, anthracene, phenanthrene, carbazole, pyrene, triphenylene, chrysene, naphthacene, biphenylene, and fluorene.

[0035] In this specification, the term "polycyclic aromatic hydrocarbon structure" refers to an aromatic structure having hydrocarbons composed of two or more aromatic rings that exhibit aromaticity, and includes fused polycyclic aromatic hydrocarbon structures having fused rings and hydrocarbon ring assembly structures in which multiple aromatic rings are directly bonded via single bonds. Note that in this specification, the term "polycyclic aromatic hydrocarbon structure" also includes heterocyclic structures in which some carbon atoms of the aromatic rings are substituted with nitrogen.

[0036] The condensed polycyclic aromatic hydrocarbon structure is not particularly limited, but examples thereof include a naphthalene structure, an anthracene structure, a phenanthrene structure, a carbazole, a pyrene structure, a triphenylene structure, a chrysene structure, a naphthacene structure, a biphenylene structure, and a fluorene structure.

[0037] The hydrocarbon ring assembly structure is not particularly limited, but examples thereof include a carbazole structure, a biphenyl structure, a terphenyl structure, a quaterphenyl structure, a binaphthalene structure, a phenylnaphthalene structure, a phenylfluorene structure, and a diphenylfluorene structure.

[0038] The polycyclic aromatic hydrocarbon structure may be substituted with a substituent. The optionally substituted substituent is not particularly limited, and examples thereof include an alkyl group, a hydroxy group, a carboxy group, and a halogen group (for example, a fluorine group, a chlorine group, a bromine group, and an iodine group). Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 1-ethyl-n-propyl group, a 1-hex ... Examples of the alkyl group include a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.Furthermore, a cyclic alkyl group can also be used as the alkyl group. Examples of cyclic alkyl groups having 1 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethyl ...2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclobutyl, Examples of such groups include 1-n-propylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group.

[0039] From the viewpoint of suitably obtaining the effects of the present invention, the polycyclic aromatic hydrocarbon structure is preferably a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a triphenylene structure, a chrysene structure, a naphthacene structure, a biphenylene structure, a fluorene structure, or a carbazole structure, more preferably a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, or a carbazole structure, and even more preferably a naphthalene structure or a carbazole structure. The polycyclic aromatic hydrocarbon structure may be one or more types, but is preferably one or two types.

[0040] The unit structure (C1) is not particularly limited, but a unit structure represented by the following formula (C1-1) can be suitably used. (In formula (C1-1), R １ represents a hydrogen atom or a methyl group. X represents an ester group or an amide group. Y represents an alkylene group having 1 to 6 carbon atoms. p and q each independently represent 0 or 1. Ar represents a monovalent group obtained by removing a hydrogen atom from naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenylene, fluorene, or carbazole, which may be substituted.

[0041] The unit structure (C1) is not particularly limited, but a unit structure represented by the following formula (C1-2) can be suitably used. (In formula (C1-2), R １ represents a hydrogen atom or a methyl group, Z represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxy group, an amino group, an amido group, an alkoxycarbonyl group, or a thioalkyl group substituted on a naphthalene ring, and n represents an integer of 0 to 7. When n is 2 or more, two or more Zs may be the same or different.

[0042] In Z, the halogen atom can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The alkyl group can be, for example, a linear or branched alkyl group having 1 to 6 carbon atoms, which may be substituted with a halogen atom or the like. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butoxy group, a t-butoxy group, an n-hexyl group, and a chloromethyl group. Examples of the alkoxy group can be, for example, an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the amide group can be, for example, an amide group having 1 to 12 carbon atoms, such as a formamide group, an acetamide group, a propionamide group, an isobutylamide group, a benzamide group, a naphthylamide group, and an acrylamide group. Examples of the alkoxycarbonyl group can be, for example, an alkoxycarbonyl group having 1 to 12 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group. The thioalkyl group is, for example, a thioalkyl group having 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a butylthio group, and a hexylthio group.

[0043] Specific examples of the structural unit (C1) represented by formula (C1-2) are as follows:

[0044] Furthermore, the unit structure (C1) is not particularly limited, but a unit structure represented by the following formula (C1-3) can be suitably used. (In formula (C1-3), Ar １ and Ar ２ each independently represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and Ar １ and Ar ２ At least one of is naphthalene, anthracene, phenanthrene, or pyrene, and Q represents a single bond or a divalent linking group.

[0045] Examples of aromatic rings having 6 to 40 carbon atoms include benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, and dibenzo[a,j]anthracene.

[0046] Examples of the divalent linking group for Q include an ether group, an ester group, and an imino group, and the imino group is preferred.

[0047] The unit structure (C1) may be of one or more types, preferably one or two types.

[0048] When the polymer contains the unit structure (C1), the molar ratio of the unit structure (C1) is preferably 10 to 90 mol %, more preferably 30 to 85 mol %, and even more preferably 40 to 80 mol %, based on all unit structures of the polymer, from the viewpoint of suitably achieving the effects of the present invention.

[0049] Polymer (A3) includes polymers described in WO 2023 / 106364, the contents of which are incorporated herein by reference in their entirety.

[0050] The molecular weight of the polymer (A3) is not particularly limited, but the weight average molecular weight determined by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) is preferably 1,500 to 100,000, and more preferably 2,000 to 50,000.

[0051] <<Polymer (A4)>> The polymer (A4) has an aromatic hydrocarbon structure having 6 to 40 carbon atoms in its main chain. Examples of such a polymer include a polymer represented by the following formula (Q): In formula (Q), Ar represents an aromatic ring group having 6 to 40 carbon atoms which may be substituted; L ０represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; T ０ represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms, ０ and T ０ Unlike n R ０ each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group; n represents an integer of 0 to 5; ＊ represents a bonding portion to a polymer or compound residue.

[0052] Examples of aromatic rings having 6 to 40 carbon atoms include benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene, and derivatives thereof. Among these, benzene, naphthalene, and anthracene are preferred.

[0053] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 1-ethyl-n-propylene group. cyclopentylene group, 1-methyl-n-pentylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples of the cyclopropylene group include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0054] Examples of the alkenylene group having 2 to 10 carbon atoms include alkylene groups having 2 to 10 carbon atoms and having at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms. Of the alkenylene groups having 2 to 10 carbon atoms, a vinylene group is preferred.

[0055] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0056] The term "optionally substituted" means that some or all of the hydrogen atoms present in the aromatic ring having 6 to 40 carbon atoms, the alkylene group having 1 to 10 carbon atoms, or the alkenylene group having 2 to 10 carbon atoms may be substituted with, for example, a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0057] The polymer (A4) is a polymer represented by the following formula (Q-1): In formula (Q-1), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L １ represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, and n represents an integer of 1 to 3, ＊ represents a bond. It is preferable that the compound has a structure represented by the following formula (I):

[0058] Examples of the structure represented by the above formula (Q-1) include the following. (In the following examples, the bond ＊ The structure of the compound is shown by replacing hydrogen atoms with the

[0059] The polymer (A4) is preferably a reaction product of the above-mentioned exemplary compound with an epoxy group-containing compound. It is also preferable that the reaction product with the epoxy group-containing compound has a repeating unit. Examples of the epoxy group-containing compound include the following.

[0060]

[0061] Examples of the polymer (A4) include the polymers described in WO 2022 / 196662. The polymer (A4) may be a polymer contained in at least one selected from resist underlayer film-forming compositions A, B, and C described in WO 2022 / 196662. For example, examples of the polymer (A4) include the polymers described as Examples A1 to A19 in WO 2022 / 196662. The contents of WO 2022 / 196662 are incorporated herein by reference to the same extent as if expressly set forth in their entirety.

[0062] The molecular weight of the polymer (A4) is not particularly limited, but the weight average molecular weight determined by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) is preferably 1,000 to 30,000, and more preferably 2,000 to 20,000.

[0063] <<Polymer (A5)>> The polymer (A5) is a reaction product of a bifunctional or higher functional compound having at least one disulfide bond and a trifunctional or higher functional compound.

[0064] The bifunctional or higher functional compound having at least one disulfide bond is, for example, a dicarboxylic acid containing a disulfide bond. The dicarboxylic acid containing a disulfide bond is represented by, for example, the following formula (1): (In formula (1), X １ and X ２ represents an alkylene group having 1 to 10 carbon atoms, which may be substituted, an arylene group having 6 to 40 carbon atoms, which may be substituted, or a combination thereof.

[0065] In the formula (1) for the polymer (A5), X １ and X ２ are preferably alkylene groups each having 1 to 3 carbon atoms.

[0066] The tri- or higher functional compound is, for example, a compound containing three or more epoxy groups. The tri- or higher functional compound is preferably a compound containing three epoxy groups. Examples of the compound containing three or more epoxy groups include a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, and a glycidyl group-containing isocyanurate.

[0067] Examples of polymer (A5) include the reaction product described in WO 2019 / 151471. This reaction product is a reaction product of a bifunctional or higher functional compound having at least one disulfide bond and a trifunctional or higher functional compound. The contents of WO 2019 / 151471 are incorporated herein by reference to the same extent as if set forth in their entirety.

[0068] The weight average molecular weight of the polymer (A5) is, for example, 1,000 to 100,000, or 1,100 to 50,000, or 1,200 to 30,000, or 1,300 to 20,000.

[0069] <<Polymer (A6)>> Polymer (A6) is a polymer containing, at its terminal, an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted with a substituent. In other words, polymer (A6) is a polymer containing, at its terminal, an aliphatic ring which may contain an —O— or —S— bond between the carbon-carbon bond and which may be substituted with a substituent.

[0070] The aliphatic ring is, for example, a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. The polycyclic aliphatic ring is, for example, a bicyclo ring or a tricyclo ring. The aliphatic ring has, for example, at least one unsaturated bond. The substituent is, for example, selected from a hydroxy group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and a carboxy group.

[0071] The polymer (A6) has, for example, at least one structural unit represented by the following formula (3) in the main chain. (In formula (3), A １ , A ２ , A ３ , A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ represents a divalent organic group, and m1 and m2 each independently represent 0 or 1.

[0072] In the formula (3) for polymer (A6), for example, Q １ represents a divalent organic group represented by the following formula (5). (In the formula, Y represents a divalent group represented by the following formula (6) or formula (7).) (In the formula, R ６ and R ７ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one 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, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms, or R ６ and R ７ are bonded to each other to form the R ６ and R ７ may form a ring having 3 to 6 carbon atoms together with the carbon atom bonded to

[0073] The polymer (A6) further contains, for example, a disulfide bond in the main chain.

[0074] Examples of polymer (A6) include the polymers described in WO 2020 / 226141. The polymers include a terminal aliphatic ring in which the carbon-carbon bond may be interrupted by a heteroatom and which may be substituted with a substituent. The contents of WO 2020 / 226141 are incorporated herein by reference to the same extent as if fully set forth herein.

[0075] The weight average molecular weight of the polymer (A6) is, for example, 2,000 to 50,000.

[0076] <<Polymer (A7)>> One example of polymer (A7) is a reaction product of compound (A) represented by formula (1) below, compound (B) having two functional groups reactive with epoxy groups, and compound (C) having one functional group reactive with epoxy groups, all dissolved in a solvent. Another example of polymer (A7) is a reaction product of compound (A) represented by formula (1) below, and compound (B) having two functional groups reactive with epoxy groups and not containing a disulfide bond, all dissolved in a solvent. Another example of polymer (A7) is a reaction product soluble in a solvent (the solvent contained in the composition for forming a resist underlayer film), obtained by reacting a mixture containing compound (A) represented by formula (1) below, compound (B) having two functional groups reactive with epoxy groups, and compound (C) having one functional group reactive with epoxy groups. (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.)

[0077] The term "soluble in a solvent" means that the reaction product remains uniformly dissolved in the solvent; for example, it means that no precipitate (including gel) of the reaction product is visible even after storage under certain conditions (for example, in the range of 5 to 40°C for one month), and that all 100 mL of the composition can be filtered using a microfilter with a pore size of 0.05 μm to 0.1 μm within 30 minutes.

[0078] A in the formula (1) for the polymer (A7) is, for example, a heterocycle. The heterocycle is, for example, a triazine ring.

[0079] The compound (B) for the polymer (A7) is a compound having two functional groups reactive with an epoxy group, which include an aliphatic ring, an aromatic ring, a heterocyclic ring, a fluorine atom, an iodine atom, or a sulfur atom.

[0080] The compound (C) relating to the polymer (A7) is a compound having one functional group reactive with an epoxy group, which contains an aliphatic ring or aromatic ring which may be substituted with a substituent.

[0081] Examples of functional groups reactive with an epoxy group include a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, an allyl group, and an acid anhydride, with a carboxy group being preferred.

[0082] The polymer (A7) includes, for example, a partial structure represented by the following formula (1-1). (In formula (1-1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring, and R １ represents a residue derived from compound (B), and * represents the bond to compound (B) or compound (C).

[0083] Polymer (A7) includes the reaction products described in WO 2022 / 075339, the contents of which are incorporated herein by reference in their entirety.

[0084] The lower limit of the weight average molecular weight of polymer (A7) is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight average molecular weight of polymer (A7) is, for example, 30,000, 20,000, or 10,000.

[0085] <<Polymer (A8)>> Polymer (A8) is a polymer having a unit structure represented by the following formula (I). (In formula (I), A １ , A ２ , A ３ , A ４ , A ５ and A ６each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ represents a divalent organic group, R １ represents a tetravalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms; L １ and L ２ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom.

[0086] R in formula (I) for polymer (A8) １ For example, includes a biphenylene structure.

[0087] The polymer (A8) contains a repeating unit represented by the following formula (a-2). (In formula (a-2), Y １ represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group; n1 T １ and n2 T ２ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be bonded to each other to bridge two benzene rings; n1 and n2 each independently represent an integer of 0 to 4; Q １ , A １ , A ２ , A ３ , A ４ , A ５ , A ６ , L １ and L ２ is Q in formula (I) １ , A １ , A ２ , A ３ , A ４ , A ５ , A ６ , L １ and L ２ are synonymous with

[0088] The polymer (A8) further has a heterocyclic structure.

[0089] Y in formulas (I) and (a-1) for polymer (A8) １ is, for example, a sulfonyl group.

[0090] The terminals of the polymer (A8) are capped with, for example, a compound. The compound includes, for example, an aliphatic ring optionally substituted with a substituent. The compound is represented, for example, by the following formulas (1) and (2). (In formulas (1) and (2), R １ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a halogeno group, or a hydroxy group, which may have a substituent; R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogeno group, or an ester group represented by -C(=O)O-X, where X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a halogeno group; R ４ represents a single bond or a divalent organic group having 1 to 8 carbon atoms; R ５ represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocycle, t represents 0 or 1, and u represents 1 or 2.

[0091] The weight average molecular weight of the polymer (A8) is preferably 500 to 50,000, more preferably 1,000 to 30,000.

[0092] Polymer (A8) includes polymers described in WO 2022 / 163673, the contents of which are incorporated herein by reference in their entirety.

[0093] <<Polymer (A9)>> The polymer (A9) is a polymer containing a repeating unit represented by the following formula (1). (In formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms. ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0094] R in formula (1) for polymer (A9) １ preferably represents the following formula (1X): (In formula (1X), R １１represents an alkylene group having 1 to 4 carbon atoms, R １２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having a total of 2 to 10 carbon atoms. * represents a bond.

[0095] In the formula (1X) for polymer (A9), R １１ preferably represents a methylene group or a 1,2-ethylene group. １２ preferably represents a hydrogen atom or an alkoxyalkyl group having a total of 2 to 6 carbon atoms.

[0096] The polymer (A9) preferably further contains a repeating unit represented by the following formula (2): (In formula (2), X represents a single bond or —COO—, and R ３ represents a monovalent organic group having 1 to 20 carbon atoms, R ４ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * represents a bond.

[0097] Preferably, X in formula (2) for polymer (A9) represents —COO—, and R ３ represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group having a cyclic structure which may have a heteroatom and having a total of 2 to 20 carbon atoms, or the following formula (2X): (In formula (2X), R ２１ represents an alkylene group having 1 to 4 carbon atoms, R ２２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having a total of 2 to 10 carbon atoms.

[0098] The linear or branched alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The monovalent group having a cyclic structure which may have a heteroatom and a total of 2 to 20 carbon atoms is preferably a monovalent group in which one hydrogen atom has been removed from a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. In formula (2X) relating to polymer (A9), R ２１preferably represents a methylene group, a 1,2-ethylene group, or a propylene group. ２２ preferably represents a hydrogen atom or an alkoxyalkyl group having a total of 2 to 6 carbon atoms.

[0099] The molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) (formula (1):formula (2)) in the polymer (A9) is preferably 30:70 to 90:10.

[0100] The molecular weight of the polymer (A9) is not particularly limited, but the weight average molecular weight determined by gel permeation chromatography is preferably from 5,000 to 100,000, and more preferably from 10,000 to 50,000.

[0101] Polymer (A9) includes polymers described in WO 2023 / 085293, the contents of which are incorporated herein by reference in their entirety.

[0102] <<Polymer (A10)>> Polymer (A10) is a polymer including at least one of a first structure and the second structure. The first structure includes a group represented by the following formula (1) directly bonded to an aromatic ring. The second structure includes a group represented by the following formula (1) directly bonded to a nitrogen atom. (In formula (1), R １ represents an alkylene group having 1 to 6 carbon atoms, R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having a total of 2 to 10 carbon atoms. * represents a bond.

[0103] The polymer (10) preferably includes, as the first structure, at least one of a structure represented by the following formula (11), a structure represented by the following formula (12), and a structure represented by the following formula (13): (In formulas (11) to (13), R １ each independently represents an alkylene group having 1 to 6 carbon atoms; R ２each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having a total of 2 to 10 carbon atoms; R ３ each independently represents an alkyl group having 1 to 6 carbon atoms. * represents a bond. In formula (11) related to polymer (A10), n1 represents an integer of 1 to 4, n2 represents an integer of 0 to 3, n3 represents an integer of 0 to 3, and n1, n2, and n3 satisfy 1≦(n1+n2+n3)≦4. In formula (12) related to polymer (A10), n1 represents an integer of 1 to 6, n2 represents an integer of 0 to 5, n3 represents an integer of 0 to 5, and n1, n2, and n3 satisfy 1≦(n1+n2+n3)≦6. In formula (13) relating to polymer (A10), n1 represents an integer of 1 to 8, n2 represents an integer of 0 to 7, and n3 represents an integer of 0 to 7, and n1, n2, and n3 satisfy the relationship 1≦(n1+n2+n3)≦8. １ If there are two or more, there are two or more R １ may be the same or different. ２ If there are two or more, there are two or more R ２ may be the same or different. ３ If there are two or more, there are two or more R ３ may be the same or different.)

[0104] The polymer (10) preferably contains, as the repeating unit containing the structure represented by formula (11), at least one of a repeating unit represented by the following formula (11-1) and a repeating unit represented by the following formula (11-2): (In formula (11-1) and formula (11-2), R １ each independently represents an alkylene group having 1 to 6 carbon atoms; R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having a total of 2 to 10 carbon atoms; R ３Each n1 independently represents an integer of 1 to 4, each n2 independently represents an integer of 0 to 3, and each n3 independently represents an integer of 0 to 3. In formula (11-1) relating to polymer (A10), X １ and X ２ Each of X independently represents a single bond, an oxygen atom, or a methylene group. １ and X ２ each independently represents a single bond, an oxygen atom, or a methylene group. ３ represents a single bond or a divalent organic group having 1 to 15 carbon atoms. In formula (11-1) relating to polymer (A10), n1, n2, and n3 satisfy 1≦(n1+n2+n3)≦4. In formula (11-2) relating to polymer (A10), n1, n2, and n3 in the left benzene ring satisfy 1≦(n1+n2+n3)≦4. In formula (11-1) and formula (11-2) relating to polymer (A10), R １ If there are two or more, there are two or more R １ may be the same or different. ２ If there are two or more, there are two or more R ２ may be the same or different. ３ If there are two or more, there are two or more R ３ may be the same or different.)

[0105] The polymer (A10) preferably contains a repeating unit represented by the following formula (14). (In formula (14), Q represents a divalent group.)

[0106] In the formula (14) relating to the polymer (A10), Q preferably represents a divalent group represented by the following formula (14-1) or an arylene group having 6 to 40 carbon atoms. (In formula (14-1), X represents a group represented by any one of the following formulas (14-1a) to (14-1c).) (In formulas (14-1a) to (14-1c), R １１ , R １２ , R １３ , R １４ , and R １５ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and 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, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. １１ and R １２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. １３ and R １４ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom.)

[0107] Examples of polymer (A10) include polymers described in WO 2023 / 085295, the contents of which are incorporated herein by reference in their entirety.

[0108] The molecular weight of the polymer (A10) is not particularly limited, but the weight average molecular weight determined by gel permeation chromatography is preferably 1,500 to 100,000, and more preferably 2,000 to 50,000.

[0109] <<Polymer (A11)>> The polymer (A11) is a polymer containing a fluorene structure.

[0110] The polymer (A11) preferably contains a partial structure represented by the following formula (1). (In formula (1), X １ represents a divalent organic group having a fluorene structure. １ , and Z ２ are each independently a single bond, —O—, —C(═O)O—, or —O—C ｍ H ２ｍ-O- (where m represents an integer of 1 to 6). １ , A ２ , A ３ , A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0111] X in formula (1) for polymer (A11) １ preferably represents a divalent organic group represented by the following formula (1-A) or (1-B): (In formulas (1-A) and (1-B), R １ , R ２ , R ５ and R ６ R each independently represents a hydroxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group, and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group, and a carboxyl group. ３ and R ４ each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms. m1 and m2 each independently represent an integer of 0 to 4. n1 and n2 each independently represent 0 or 1. When n1 is 0, o1 represents an integer of 0 to 4. When n1 is 1, o1 represents an integer of 0 to 6. When n2 is 0, o2 represents an integer of 0 to 4. When n2 is 1, o2 represents an integer of 0 to 6. R １ ~R ６ When there are multiple R １ ~R ６ Each R may be the same or different. ５ and one R ６ may be taken together to form an —O— bond. * represents a bond.)

[0112] The polymer (A11) preferably further contains at least one of a partial structure represented by the following formula (2-1) and a partial structure represented by the following formula (2-2). (In formula (2-1), X １１ represents a group represented by any one of the following formulas (2-1-1) to (2-1-3): １１ and Z １２ Each of Q independently represents a single bond or a divalent group represented by the following formula (2-1-4): １ represents a single bond or a divalent organic group. p1 and p2 each independently represent 0 or 1. (In formulas (2-1-1) to (2-1-3), R １１ ~R １５ R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one monovalent 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, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. １１ and R １２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. １３ and R １４ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom. (In formula (2-1-4), m1 represents an integer of 1 to 4, m2 represents 0 or 1, *3 represents a bond bonded to the nitrogen atom, and *4 represents a bond.)

[0113] Polymer (A11) includes polymers described in WO 2023 / 182408, the contents of which are incorporated herein by reference in their entirety.

[0114] The molecular weight of the polymer (A11) is not particularly limited, but the weight average molecular weight determined by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) is preferably 1,500 to 100,000, and more preferably 2,000 to 50,000.

[0115] <<Polymer (A12)>> The polymer (A12) is a polymer having a structure represented by the following formula (1) or (2) at the end of the polymer chain. (In the above formulas (1) and (2), X is a divalent organic group, A is an aryl group having 6 to 40 carbon atoms, and R １ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ２ and R ３ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 40 carbon atoms, n1 and n3 are each independently an integer of 1 to 12, and n2 is an integer of 0 to 11.

[0116] In the formulas (1) and (2) for polymer (A12), X is preferably an ester bond or an ether bond. In the formulas (1) and (2) for polymer (A12), A is preferably a group derived from benzene, naphthalene, or anthracene. In the formula (2) for polymer (A12), R ２ and R ３ is a hydrogen atom. In the formula (1) relating to the polymer (A12), n2 is preferably 0.

[0117] The polymer (A12) preferably has a structural unit represented by the following formula (3): (In formula (3), A １ , A ２ , A ３, A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group; Y １ is expressed by equation (4), equation (5), equation (6) or equation (7): ((In formulas (4) to (7), R ４ and R ５ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is optionally substituted with at least one 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, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; and R ４ and R ５ may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R ６ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one 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, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; and Q represents a group represented by formula (8) or (9): (In formulas (8) and (9), Q １ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group are each optionally substituted with at least one 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, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n4 and n5 each independently represent an integer of 0 or 1; Y ２ represents formula (4), formula (5) or formula (7).

[0118] The polymer having a structural unit represented by formula (3) for polymer (A12) is preferably a polymer having a compound represented by the following formula (10) and a compound represented by the following formula (11) as comonomers. (In formulas (10) and (11), A １ , A ２ , A ３ , A ４ , A ５ , A ６ , Y １ and Q have the same meaning as defined in formula (3).

[0119] The polymer having a structural unit represented by formula (3) for polymer (A12) is preferably a polymer having a compound represented by the following formula (12) and a compound represented by the following formula (13) as comonomers. (In the formula, A １ , A ２ , A ３ , A ４ , A ５ , A ６ , Y １ and Q have the same meaning as defined in formula (3).

[0120] The molecular weight of the polymer (A12) is, for example, 1,000 to 200,000, or 1,200 to 100,000, or 1,500 to 30,000, or 2,000 to 20,000, or 2,000 to 4,000, as the weight average molecular weight.

[0121] The lower limit of the weight average molecular weight of the polymer (A) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight average molecular weight of the polymer (A) is, for example, 30,000, 20,000, or 10,000.

[0122] 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.

[0123] <Compound (B)> Compound (B) has a polymerizable multiple bond. Examples of the polymerizable multiple bond include a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, and a carbon-nitrogen triple bond. Among these, from the viewpoint of suitably achieving the effects of the present invention, a carbon-carbon double bond and a carbon-carbon triple bond are preferred. Examples of the group having a polymerizable multiple bond in compound (B) include a (meth)acryloyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, and an allyl group. The number of polymerizable multiple bonds in compound (B) may be one or two or more.

[0124] Examples of the group having a polymerizable multiple bond that the compound (B) has include a group represented by the following formula (BI) and a group represented by the following formula (B-II). (In formulas (BI) and (B-II), R １１ ~R １４ each independently represents a hydrogen atom, a halogen atom, or an organic group having 1 to 6 carbon atoms. * represents a bond.

[0125] R in formula (BI) and formula (B-II) １１ ~R １４ Examples of the halogen atom in R in formula (BI) and formula (B-II) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １１ ~R １４ Examples of the organic group having 1 to 6 carbon atoms in the formula (R) include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxycarbonylalkyl group having 3 to 6 carbon atoms (R ａ -C(=O)-R ｂ - group: R ａ represents an alkyl group having 1 to 4 carbon atoms, and R ｂ represents an alkylene group having 1 to 4 carbon atoms), an acylamino group having 2 to 6 carbon atoms (R ａ -C(=O)-N(H)- group: R ａ represents an alkyl group having 1 to 5 carbon atoms.

[0126] R in formula (BI) １１and R １２ is preferably a hydrogen atom. １３ is preferably a hydrogen atom or a methyl group. １４ is preferably a hydrogen atom.

[0127] The compound (B) may be a low molecular weight compound or a high molecular weight compound, and therefore, the compound (B) may be a polymer.

[0128] The weight average molecular weight of the compound (B) is not particularly limited, but the lower limit is, for example, 500, 600, or 1,000. The upper limit of the weight average molecular weight of the compound (B) is, for example, 10,000, 7,000, or 4,000.

[0129] The weight average molecular weight of the compound (B) is preferably smaller than the weight average molecular weight of the polymer (A).

[0130] The compound (B) is, for example, a reaction product of a reactant containing a compound (B-1) having an epoxy group and a compound (B-2) having a polymerizable multiple bond and capable of reacting with the epoxy group.

[0131] Compound (B) is, for example, a reaction product of a reactant containing compound (B-3) having a hydroxy group and compound (B-4) having a polymerizable multiple bond and capable of reacting with the hydroxy group.

[0132] <<Compound (B-1)>> The compound (B-1) having an epoxy group is not particularly limited as long as it has an epoxy group. The number of epoxy groups in the compound (B-1) is not particularly limited and may be one or two or more, but two or more is preferred, and two to four is more preferred.

[0133] The molecular weight of the compound (B-1) is not particularly limited, but is preferably 500 or less.

[0134] Examples of the compound (B-1) include compounds represented by the following formulas (B1) to (B15).

[0135] In formulas (B1) to (B3), E １is a group represented by the following formula (b1): ２ is a group represented by the following formula (b2) or a group represented by the following formula (b3). (In formula (b1), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is 1 or 2, and when m3 is 1, m1 and m2 are not 0 at the same time. In formula (b2), m5 is an integer of 0 to 4, m6 is 0 or 1, m7 is 0 or 1, and m8 is 1 or 2. In formula (b3), m9 is an integer of 0 to 4. * represents a bond.)

[0136] In formulas (B1) and (B2), R １ａ and R ２ａ each independently represents a hydrogen atom; an alkyl group of 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; an alkenyl group of 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; an alkynyl group of 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; a benzyl group or a phenyl group, and the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group of 1 to 6 carbon atoms, a halogen atom, an alkoxy group of 1 to 6 carbon atoms, a nitro group, a cyano group and an alkylthio group of 1 to 6 carbon atoms.

[0137] In formula (B3), R ３ａ represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom; a benzyl group; a phenyl group; or any of the above E １ wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms.

[0138] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group. Cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2- Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3 -ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group.

[0139] Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethylethenyl, 1 ...ethyl-2-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-1-propenyl, 1-methyl-2-propenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethenyl, 1-ethyl-2-propylethen methyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl -1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group , 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i- Examples of the cyclopentyl group include a propyl-2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group.

[0140] Examples of the alkynyl group having 2 to 10 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 4-methyl-1-pentynyl group, and a 3-methyl-1-pentynyl group.

[0141] The phrase "optionally interrupted by an oxygen atom or a sulfur atom" means, for example, that a carbon atom in the saturated carbon chain of the alkyl group, alkenyl group, or alkynyl group is replaced with an oxygen atom or a sulfur atom. For example, in an alkyl group, alkenyl group, or alkynyl group, when any carbon atom is replaced with an oxygen atom, the group contains an ether bond, and when any carbon atom is replaced with a sulfur atom, the group contains a thioether bond.

[0142] Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0143] Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-but ... Examples of the alkyl group include a 1-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.

[0144] Examples of the alkylthio group having 1 to 6 carbon atoms include an ethylthio group, a butylthio group, and a hexylthio group.

[0145] In formulas (B4) to (B12), R ４ａ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. In formulae (B6) and (B11), -W- represents a single bond, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -CO-, -O-, -S- or SO ２ In formula (B13), X represents an alkylene group having 1 to 6 carbon atoms. In formula (B14), R ５ａ represents an alkylene group having 1 to 3 carbon atoms.

[0146] In formula (B4), n1 represents an integer of 2 to 4. In formula (B5), n2 represents an integer of 2 to 4. In formula (B6), n3 and n4 each independently represent an integer of 0 to 4, and n3 + n4 is 2 to 4. In formula (B7), n5 represents an integer of 2 to 4. In formula (B8), n6 and n7 each independently represent an integer of 0 to 4, and n6 + n7 is 2 to 4. In formula (B9), n8 to n11 each independently represent an integer of 0 to 4, and n8 + n9 + n10 + n11 is 2 to 4. In formula (B10), n12 represents an integer of 2 to 4. In formula (B11), n13 and n14 each independently represent an integer of 0 to 4, and n13 + n14 is 2 to 4. In formula (B12), n15 represents an integer of 2 or 3. In formula (B14), n16 represents an integer of 2 to 6. In formula (B15), n17 represents an integer of 1 to 4.

[0147] Examples of the alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms include the same as those mentioned above.

[0148] Specific examples of the compound represented by formula (B1) include the following compounds.

[0149] Specific examples of the compound represented by formula (B2) include the following compounds.

[0150] Specific examples of the compound represented by formula (B3) include the following compounds.

[0151] Specific examples of the compound represented by formula (B4) include the following compounds.

[0152] Specific examples of the compound represented by formula (B5) include the following compounds.

[0153] Specific examples of the compound represented by formula (B6) include the following compounds.

[0154] Specific examples of the compound represented by formula (B7) include the following compounds.

[0155] Specific examples of the compound represented by formula (B8) or the compound represented by formula (B9) include the following compounds.

[0156] Specific examples of the compound represented by formula (B10) include the following compounds.

[0157] Specific examples of the compound represented by formula (B11) include the following compounds.

[0158] Specific examples of the compound represented by formula (B12) include the following compounds.

[0159] Specific examples of the compound represented by formula (B13) include the following compounds.

[0160] Specific examples of the compound represented by formula (B14) include the following compounds.

[0161] Specific examples of the compound represented by formula (B15) include the following compounds.

[0162] Other specific examples of the compound (B-1) include the following compounds:

[0163] <<Compound (B-2)>> The compound (B-2) has a polymerizable multiple bond. The compound (B-2) is a compound capable of reacting with an epoxy group. In other words, the compound (B-2) has a group capable of reacting with an epoxy group.

[0164] The number of polymerizable multiple bonds that the compound (B-2) has may be 1 or 2 or more, but is preferably 1. As the group having a polymerizable multiple bond that the compound (B-2) has, from the viewpoint of more suitably obtaining the effects of the present invention, the group represented by the formula (BI) or the group represented by the formula (B-II) is preferred.

[0165] The number of "groups capable of reacting with an epoxy group" contained in the compound (B-2) may be 1 or 2 or more, but is preferably 1. Examples of the group capable of reacting with an epoxy group include a carboxy group, an amino group, a phenolic hydroxy group, and an acid dianhydride group.

[0166] The compound (B-2) may or may not have a ring structure, but preferably does not have a ring structure. Examples of the ring structure include an aliphatic ring and an aromatic ring.

[0167] Examples of the compound (B-2) include compounds represented by the following formulas (B-2-1) to (B-2-6). (In formulas (B-2-1) to (B-2-6), R １１ ~R １４ represents R in formula (BI) and formula (B-II), respectively. １１ ~R １４ X represents -O- or -N(R)- (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Y １ each independently represents an organic group having 1 to 10 carbon atoms. ２ each independently represents a single bond or an organic group having 1 to 6 carbon atoms.

[0168] Y １ The organic group having 1 to 10 carbon atoms in the formula Y may or may not have a heteroatom. １ The organic group having 1 to 10 carbon atoms in Y may or may not have an ester bond. １In the above formula, examples of the organic group having 1 to 10 carbon atoms include alkylene groups having 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic, or may be a combination of two or more of these.

[0169] Y ２ The organic group having 1 to 6 carbon atoms in the formula Y may or may not have a heteroatom. ２ In the above formula, examples of the organic group having 1 to 6 carbon atoms include alkylene groups having 1 to 6 carbon atoms. The alkylene group may be linear, branched, or cyclic, or may be a combination of two or more of these.

[0170] Specific examples of the compound (B-2) include the following compounds:

[0171] Among these, acrylic acid and methacrylic acid are preferred as the compound (B-2) from the viewpoint of suitably achieving the effects of the present invention.

[0172] The reaction of the reactant containing compound (B-1) and compound (B-2) may be carried out, for example, in the presence of a catalyst. Examples of the catalyst include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10 mass% based on the total mass of the reaction raw materials used in the reaction. Optimal reaction temperature and time conditions can be selected, for example, from the ranges of 50 to 160°C and 2 to 50 hours.

[0173] The compounding ratio of the compounds (B-1) and (B-2) during the reaction is preferably such that the amount of groups reactive with epoxy groups in the compound (B-2) is 1 mole or more relative to 1 mole of epoxy groups in the compound (B-1), and more preferably 1 mole or more and 1.5 moles or less.

[0174] <<Compound (B-3)>> The compound (B-3) having a hydroxy group is not particularly limited as long as it has a hydroxy group. The number of hydroxy groups in the compound (B-3) is not particularly limited and may be one or two or more, but is preferably three or more, and more preferably three to six.

[0175] The compound (B-3) having a hydroxy group may or may not have an epoxy group. The compound (B-3) having a hydroxy group may be, for example, an amino group (—NH ２ ), or an amino group (—NH ２ ) may not be present.

[0176] Examples of the compound (B-3) include compounds having three hydroxy groups, compounds having four hydroxy groups, compounds having five hydroxy groups, compounds having six hydroxy groups, compounds having eight hydroxy groups, etc. Examples of the compound having three hydroxy groups include trimethylolpropane, trimethylolbutane, 2,3-di(2'-hydroxyethyl)-cyclohexane-1-ol, hexane-1,2,6-triol, 1,1,1-tris(hydroxymethyl)ethane, 3-(2'-hydroxyethoxy)propane-1,2-diol, 3-(2'-hydroxypropoxy)-propane-1,2-diol, 2-(2'-hydroxyethoxy)-hexane-1,2-diol, Examples of compounds having four hydroxy groups include diglycerol, di(trimethylolpropane), pentaerythritol, and 1,1,4-tris-(dihydroxyphenyl)butane. Examples of compounds having five hydroxy groups include triglycerol. Examples of compounds having six hydroxy groups include dipentaerythritol. An example of a compound having eight hydroxy groups is tripentaerythritol.

[0177] The molecular weight of the compound (B-3) is not particularly limited, but is preferably 500 or less.

[0178] <<Compound (B-4)>> Compound (B-4) has a polymerizable multiple bond. Compound (B-4) is a compound capable of reacting with a hydroxy group. In other words, compound (B-4) has a group capable of reacting with a hydroxy group. When compound (B-3) has a functional group other than a hydroxy group, the group capable of reacting with a hydroxy group that compound (B-4) has may be capable of reacting with the functional group.

[0179] The number of polymerizable multiple bonds that the compound (B-4) has may be 1 or 2 or more, but is preferably 1 or 2. From the viewpoint of more suitably obtaining the effects of the present invention, the group having a polymerizable multiple bond that the compound (B-4) has is preferably a group represented by formula (BI) or a group represented by formula (B-II).

[0180] The number of "groups capable of reacting with a hydroxy group" contained in the compound (B-4) may be 1 or 2 or more, but is preferably 1. Examples of the group capable of reacting with a hydroxy group include an isocyanate group.

[0181] Examples of the compound (B-4) include compounds represented by the following formula (B-4-1). (In formula (10), R １１ represents a linear or branched saturated aliphatic group having 1 to 10 carbon atoms. １２ represents a hydrogen atom or a methyl group, R １３ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms; R １４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group.

[0182] Examples of the compound represented by formula (B-4-1) include compounds represented by the following formula (B-4-1-1). (In formula (B-4-1-1), R １２ represents a hydrogen atom or a methyl group, R ２０ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0183] Compound (B-4) may be a commercially available product, such as Karenz-BEI (manufactured by Resonac Co., Ltd.).

[0184] The reaction of the reactant containing compound (B-3) and compound (B-4) may be carried out, for example, in the presence of a catalyst. The catalyst is, for example, an amine such as triethylamine. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10 mass% based on the total mass of the reaction raw materials used in the reaction. The optimum reaction temperature and time can be selected, for example, from the ranges of 50 to 160°C and 2 to 50 hours.

[0185] The compounding ratio of the compounds (B-3) and (B-4) during the reaction is preferably such that the amount of groups reactive with hydroxy groups in the compound (B-4) is 1 mole or more relative to 1 mole of hydroxy groups in the compound (B-3), and more preferably 1 mole or more and 1.5 moles or less.

[0186] The content of the compound (B) 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, the content of the polymer (A) is preferably greater than the content of the compound (B) (less than 100% by mass relative to the polymer (A)), more preferably 3% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass relative to the polymer (A).

[0187] The content of the compound (B) 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 2% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, based on the film-constituting components.

[0188] <Solvent (C)> The solvent (C) 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] Among these solvents (C), alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0193] These solvents (C) may be used alone or in combination of two or more.

[0194] The mass proportion of the organic solvent in the solvent (C) is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0195] The content of the solvent (C) 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.

[0196] <Crosslinking Agent (D)> The crosslinking agent (D) is not particularly limited. The crosslinking agent (D) has a structure different from the polymer (A) and the compound (B).

[0197] The crosslinking agent (D) 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.

[0198] Examples of the crosslinking agent (D) 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.

[0199] 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.

[0200] The crosslinking agent (D) 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0206] 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).

[0207] (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.

[0208] (In formula (3d), R １ represents a methyl group or an ethyl group.)

[0209] 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.

[0210] 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.

[0211] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (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 +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n５ an integer ≦3, n ６ is 1≦n ６ n is an integer ≦4 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.

[0212] 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. (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, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６an 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.

[0213] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0214] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: 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.

[0215] 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.

[0216] The molecular weight of the crosslinking agent (D) is not particularly limited, but is preferably 500 or less.

[0217] The content of the crosslinking agent (D) 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, based on the total amount of the polymer (A) and the compound (B).

[0218] <Curing Catalyst (E)> The curing catalyst (E) 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.

[0219] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0220] 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.

[0221] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0222] 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.

[0223] The curing catalyst (E) may be used alone or in combination of two or more.

[0224] When the curing catalyst (E) is used, the content of the curing catalyst (E) relative to the crosslinking agent (D) is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0225] <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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] (Resist Underlayer Film) The resist underlayer film 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 the applied composition.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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 ( 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).

[0235] 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)

[0236] (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.

[0237] (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.

[0238] 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.

[0239] Typically, a resist film is formed on the resist underlayer film. The film thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0240] 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).

[0241] 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.

[0242] Examples of the resist composition include the following compositions.

[0243] 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):

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] [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.]

[0250] Examples of the resist film include the following.

[0251] 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:

[0252] (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.

[0253] Examples of resist materials include the following:

[0254] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2):

[0255] (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.

[0256] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0257] (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.

[0258] 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):

[0259] [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.

[0260] 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).

[0261] [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.

[0262] 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.

[0263] A coating comprising a metal oxo-hydroxo network having organic ligands with metal carbon and / or metal carboxylate bonds.

[0264] Inorganic oxo / hydroxo-based compositions.

[0265] 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.

[0266] 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.

[0267] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0277] The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 8 below 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)

[0278] Synthesis Example 1 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.45 g of diethylbarbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 56.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by reflux heating for 10 hours to obtain a solution containing polymer 1. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether. GPC analysis showed that the obtained polymer 1 had a weight average molecular weight of 10,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0279]

[0280] Synthesis Example 2 5.00 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.33 g of 2-hydroxypropyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.50 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 29.94 g of propylene glycol monomethyl ether (hereinafter, sometimes referred to as "PGME") in a reaction vessel, and then added to 21.39 g of PGME that had been heated and maintained at 130°C. The reaction was carried out for 16 hours to obtain a solution containing polymer 2. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. GPC analysis showed that the obtained polymer 2 had a weight average molecular weight of 7,900 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1c) and (1d).

[0281]

[0282] Synthesis Example 3 3.00 g of Denacol Ex622 (manufactured by Nagase ChemteX Corporation), 1.20 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.18 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.03 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 10.30 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 48 hours to obtain a solution containing polymer 3. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the obtained polymer 3 had a weight average molecular weight of 3,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1e) and (1f).

[0283]

[0284] Synthesis Example 4 3.00 g of Denacol Ex622 (manufactured by Nagase ChemteX Corporation), 1.44 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.18 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.03 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 10.85 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 48 hours to obtain a solution containing polymer 4. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. GPC analysis showed that the obtained polymer 4 had a weight average molecular weight of 3,200 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1e) and (1g).

[0285]

[0286] Synthesis Example 5 3.00 g of TEPIC-SS (manufactured by Nissan Chemical Industries, Ltd.), 2.39 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.35 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.01 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 8.78 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 24 hours to obtain a solution containing polymer 5. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. When GPC analysis was performed, the obtained polymer 5 had a weight average molecular weight of 730 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1h) and (1f).

[0287]

[0288] Synthesis Example 6 3.00 g of TEPIC-SS (Nissan Chemical Industries, Ltd.), 2.85 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), 0.35 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to 9.47 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 24 hours to obtain a solution containing polymer 6. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. When GPC analysis was performed, the obtained polymer 6 had a weight average molecular weight of 770 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1h) and (1g).

[0289]

[0290] Synthesis Example 7 6.00 g of EPLICON-HP4700 (DIC Corporation), 5.50 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), 0.48 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to 27.98 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was heated to 100°C for 24 hours to obtain a solution containing Polymer 7. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether acetate was good. GPC analysis revealed that the resulting Polymer 7 had a weight-average molecular weight of 3,000 in terms of standard polystyrene. The polymer obtained in this Synthesis Example had structural units represented by the following formulas (1i) and (1g).

[0291]

[0292] Synthesis Example 8 4.00 g of Karenz-BEI (manufactured by Resonac Inc.), 0.51 g of tris(hydroxymethyl)aminomethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.17 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 11.25 g of propylene glycol monomethyl ether acetate and dissolved. The reaction vessel was then purged with nitrogen, and the mixture was heated to 105°C for 18 hours to obtain a solution containing polymer 8. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether acetate. GPC analysis revealed that the resulting polymer 8 had a weight-average molecular weight of 1,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1j) and (1k).

[0293]

[0294] [Preparation of Compositions for Forming Resist Underlayer Films] (Examples and Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 3 and 8 above were mixed in the proportions shown in Table 1, and the mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare compositions for forming resist underlayer films of Example 1 and Comparative Examples 1 and 2, respectively.

[0295] The abbreviations in Table 1 are as follows: PL-LI: tetramethoxymethyl glycoluril PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- (structural formula below)

[0296] Py-PSA: Pyridinium-p-hydroxybenzenesulfonic acid PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0297]

[0298] [Elution Test in Photoresist Solvent] Each of the resist underlayer film-forming compositions of Example 1, Comparative Example 1, and Comparative Example 2 was applied to a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer film (film thickness 5 nm). These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio), which is a solvent used in photoresists. A change in film thickness of less than 5 Å was rated as "good," and a change in film thickness of 5 Å or more was rated as "poor." The results are shown in Table 2.

[0299]

[0300] [Formation of Negative Resist Pattern by EUV Exposure] The resist underlayer film-forming compositions of Example 1, Comparative Example 1, and Comparative Example 2 were each applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a 5 nm-thick resist underlayer film. An EUV resist solution (tin oxide-based resist) was spin-coated onto the resist underlayer film and heated at 130°C for 1 minute to form an EUV resist layer. The resist was then exposed using an ASML EUV exposure system (NXE3300B) under conditions of NA = 0.33, σ = 0.67 / 0.90 (outer / inner), and dipole. During exposure, the EUV resist was exposed through a mask configured so that the columnar patterns (hereinafter referred to as pillars) of the EUV resist and the width between the pillars were 38 nm (X direction) and 66 nm (Y direction) after development as described below. After exposure, post-exposure baking (PEB, 170°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate, development using an organic solvent (propylene glycol monomethyl ether acetate) for 60 seconds, and rinsing to form a resist pattern with a CD size of 22 nm. A scanning electron microscope (CG6100, manufactured by Hitachi High-Technologies Corporation) was used to measure the length of the resist pattern. The photoresist pattern thus obtained was observed from above and evaluated. When a pillar pattern with a CD size of 22.5 nm was formed, it was rated as "good," and when pattern collapse was observed, it was rated as "poor." The exposure dose at which a pillar pattern with a CD size of 22 nm was formed was defined as the optimal exposure dose, and the exposure dose (mJ / cm) at that time was determined as follows: ２ ) are shown in Table 3.

[0301]

[0302] The effects of improving the sensitivity and adhesion in a pillar pattern with a CD size of 22 nm were confirmed in Example 1, compared with Comparative Examples 1 and 2. These results demonstrate that a resist underlayer film containing a compound having a polymerizable multiple bond can improve the sensitivity and adhesion, and has good pattern formation ability.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A), a compound having a polymerizable multiple bond (B), and a solvent (C).

2. The composition for forming a resist underlayer film according to claim 1, wherein the compound (B) is a reaction product of a reactant containing a compound (B-1) having an epoxy group and a compound (B-2) having a polymerizable multiple bond and capable of reacting with an epoxy group.

3. The composition for forming a resist underlayer film according to claim 1, wherein the compound (B) is a reaction product of a reactant containing a compound (B-3) having a hydroxy group and a compound (B-4) having a polymerizable multiple bond and capable of reacting with a hydroxy group.

4. The composition for forming a resist underlayer film according to claim 1, wherein the content of the polymer (A) is greater than the content of the compound (B).

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

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

7. The composition for forming a resist underlayer film according to claim 6, wherein the crosslinking agent (D) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

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

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

10. The composition for forming a resist underlayer film according to claim 1, which is used for forming an underlayer film of a metal-containing resist.

11. 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 10.

12. A laminate comprising: a semiconductor substrate; and the resist underlayer film according to claim 11.

13. A method for manufacturing a semiconductor device, 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 10; and a step of forming a resist film on the resist underlayer film.

14. A pattern forming 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 10; 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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