Composition for forming resist underlayer film

Abstract

The present invention relates to a composition for forming a resist underlayer film, which contains a polymer having a structural unit (A) having a polycyclic aromatic structure and a crosslinking agent, and is used in lithography using a photoresist film or an electron beam resist film, and forming a lower layer film of the resist film on a nitrogen atom-containing substrate.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition for forming an underlayer film for a resist, an underlayer film, and a method for manufacturing a semiconductor element. BACKGROUND

[0002] With the development of semiconductor manufacturing processes and the miniaturization of large-scale integrated circuits (LSI), fine processing is also employed in photolithography using a resist composition. Specifically, a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, active light such as ultraviolet light is irradiated thereon through a mask pattern on which a pattern of a device is drawn, development is performed, and the resulting photoresist pattern is used as a protective film for etching treatment of the substrate, whereby a fine concavo-convex corresponding to the photoresist pattern is formed on the surface of the substrate.

[0003] For fine processing using such a resist composition, in order to further improve the precision, high quality and improvement of characteristics of the underlayer film for a resist are required. For example, in the case where a substrate or a film of a substrate on which an underlayer film for a resist is formed contains a nitrogen atom, an amine component diffuses from the substrate, and the resolution of the resist sometimes decreases (Patent Documents 1 to 3).

[0004] PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: Japanese Patent Application Laid-Open No. 2008-39811 Patent Document 2: Japanese Patent Application Laid-Open No. 2008-39815 Patent Document 3: Japanese Patent Application Laid-Open No. 2010-134437 SUMMARY

[0005] PROBLEMS TO BE SOLVED BY THE INVENTION The present application provides a composition for forming an underlayer film for a resist, which can form a photoresist pattern with good precision even when a substrate containing a nitrogen atom is used, and which can be used as an antireflection film at the time of exposure. Furthermore, the present application provides a composition which, after an underlayer film for a resist formed by the composition of the present application is formed on a substrate, can suppress diffusion of an amine component from the substrate and a decrease in precision of a photoresist pattern during a period of, for example, several days or more before pattern formation.

[0006] MEANS OF SOLVING THE PROBLEMS The present inventors and others have conducted intensive studies in order to solve the above problems, and as a result, have found that the above problems can be solved, thereby completing the present application having the following gist.

[0007] That is, the present application comprises the following modes.

[0008] [1] A composition for resist underlayer film formation, comprising a polymer and a crosslinking agent, The polymer has a structural unit (A) having a polycyclic aromatic structure, The composition for resist underlayer film formation is used for forming an underlayer film of a resist film on a substrate containing a nitrogen atom in photolithography using a photoresist film or an electron beam resist film.

[0009] [2] The composition for resist underlayer film formation according to [1], wherein the polymer has the polycyclic aromatic structure in a side chain of the polymer.

[0010] [3] The composition for resist underlayer film formation according to [1] or [2], wherein the polycyclic aromatic structure is selected from naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, tetracene, biphenalene, fluorene, and carbazole, which can be substituted.

[0011] [4] The composition for resist underlayer film formation according to any one of [1] to [3], wherein the unit structure (A) is a unit structure represented by the following formula (A-1).

[0012] [Chemical Formula 1] ; (In formula (A-1), R 1 represents a hydrogen atom or a methyl group. X 1 represents a single bond, an ester group, or an amide group. Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms. Ar represents a monovalent group obtained by removing a hydrogen atom from naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, tetracene, biphenalene, fluorene, or carbazole, which can be substituted.) [5] The composition for resist underlayer film formation according to any one of [1] to [4], wherein the polymer further has a unit structure (B) having a reactive group, The crosslinking agent has a functional group capable of reacting with the reactive group.

[0013] [6] The composition for resist underlayer film formation according to [5], wherein the unit structure (B) is at least any one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2).

[0014] [Chemical Formula 2] ; (In formula (B-1), R 11 represents a hydrogen atom or a methyl group. X 11 represents an ester group or an amide group. R 12 represents a monovalent group having 1 to 12 carbon atoms having the reactive group.

[0015] In formula (B-2), R 13 represents a monovalent group having 1 to 12 carbon atoms with the reactive group. [7] The resist underlayer film-forming composition according to any one of [1] to [6], wherein the polymer further has at least either one of a unit structure (C) selected from a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) from a maleimide structure.

[0016] [8] The resist underlayer film-forming composition according to [7], wherein The unit structure (C-1) is a unit structure represented by the following formula (C-1-1), The unit structure (C-2) is a unit structure represented by the following formula (C-2-1).

[0017] [Chem. 3] ; (In formula (C-1-1), R 21 represents a hydrogen atom or a methyl group. X 21 represents a single bond, an ester group, or an amide group. Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms. R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In the case where R 22 may be the same or different. 22 may be the same or different.

[0018] In formula (C-1-2), R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which can be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which can be substituted with a halogen atom. [9] The resist underlayer film-forming composition according to any one of [1] to [8], wherein the molar ratio of the unit structure (A) with respect to the total unit structures of the polymer is 40 mol% or more.

[0019]

[10] The resist underlayer film-forming composition according to any one of [5] to [9], wherein the molar ratio of the unit structure (B) with respect to the total unit structures of the polymer is 5 mol% to 40 mol%.

[0020]

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

[10] , wherein the polymer further has a unit structure (B) having a reactive group, and at least any one unit structure (C) selected from a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) from a maleimide structure, the crosslinking agent has a functional group capable of reacting with the reactive group, the unit structure (A) is a unit structure represented by the following formula (A-1), the unit structure (B) is at least any one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2), the unit structure (C-1) is a unit structure represented by the following formula (C-1-1), the unit structure (C-2) is a unit structure represented by the following formula (C-2-1), the unit structure (A) has a molar ratio of 40 mol% or more with respect to the total unit structures of the polymer, the unit structure (B) has a molar ratio of 5 mol% to 40 mol% with respect to the total unit structures of the polymer.

[0021] [Chemical Formula 4] ; (In formula (A-1), R 1 represents a hydrogen atom or a methyl group. X 1 represents a single bond, an ester group, or an amide group. Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms. Ar represents a monovalent group obtained by removing a hydrogen atom from naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenalene, fluorene, or carbazole, which can be substituted.) [Chemical Formula 5] ; (In formula (B-1), R 11 represents a hydrogen atom or a methyl group. X 11 represents an ester group or an amide group. R 12 represents a monovalent group having 1 to 6 carbon atoms having the reactive group.

[0022] In formula (B-2), R 13 represents a monovalent group having 1 to 6 carbon atoms having the reactive group.) [Chemical Formula 6] ; (In formula (C-1-1), R 21 represents a hydrogen atom or a methyl group. X 21represents a single bond, an ester group, or an amide group. Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms. R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In R 22 When there are two or more R 22 may be the same or different.

[0023] In formula (C-1-2), R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which can be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which can be substituted with a halogen atom.

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

[11] , wherein the content of the crosslinking agent is 20% to 50% by mass of the polymer.

[0024]

[13] An underlayer film formed on the nitrogen atom-containing substrate using the composition for resist underlayer film formation according to any one of [1] to

[12] .

[0025]

[14] The underlayer film according to

[13] , having a film thickness of less than 10 nm.

[0026]

[15] A method for manufacturing a substrate with a resist pattern, comprising the steps of: a step of forming an underlayer film on the nitrogen atom-containing substrate using the composition for resist underlayer film formation according to any one of [1] to

[12] , a step of forming either a photoresist film or an electron beam resist film on the underlayer film, and a step of subjecting the resist film to light irradiation or electron beam irradiation, followed by developing the resist film to obtain a resist pattern.

[0027]

[16] The method for manufacturing a substrate with a resist pattern according to

[15] , comprising a step of forming the resist film after the underlayer film is formed, after 12 hours or more have passed.

[0028]

[17] A method for manufacturing a semiconductor element, comprising the steps of: a step of forming an underlayer film on the nitrogen atom-containing substrate using the composition for resist underlayer film formation according to any one of [1] to

[12] , a step of forming either a photoresist film or an electron beam resist film on the underlayer film, a step of subjecting the resist film to light irradiation or electron beam irradiation, followed by developing the resist film to obtain a resist pattern, and a step of etching the underlayer film using the resist pattern as a mask to form a patterned underlayer film.

[0029] Effects of Invention According to the present application, a resist underlayer film capable of inhibiting a decrease in resolution of a resist caused by diffusion of an amine component can be formed. In addition, according to the present application, a resist underlayer film in which resolution is not easily decreased even when a prescribed period of time elapses after the resist underlayer film is formed on a substrate before pattern formation can be formed. DETAILED DESCRIPTION

[0030] (Resist underlayer film-forming composition) The resist underlayer film-forming composition of the present application is used to form a lower layer film of a resist film on a substrate containing a nitrogen atom in photolithography using a photoresist film or an electron beam resist film.

[0031] The resist underlayer film-forming composition of the present application contains a polymer and a crosslinking agent.

[0032] The polymer has a unit structure (A) having a polycyclic aromatic structure.

[0033] The resist underlayer film-forming composition contains a polymer and a crosslinking agent, and the polymer has a unit structure (A) having a polycyclic aromatic structure, whereby a resist underlayer film in which a decrease in resolution of a resist is inhibited can be formed. In addition, even when a prescribed period of time elapses after the resist underlayer film is formed, a resist underlayer film in which resolution is not easily decreased can be formed.

[0034] The prescribed period of time is, for example, 12 hours or more, 24 hours or more, 48 hours or more, 72 hours or more, or 92 hours or more. The storage temperature is, for example, 20°C to 30°C, and the storage humidity is, for example, 30 to 70% RH, 30 to 60% RH, or 35 to 55% RH.

[0035] <Polymers> The polymer has a unit structure (A) having a polycyclic aromatic structure. The polymer preferably has a polycyclic aromatic structure in a side chain.

[0036] In addition, the polymer preferably has a unit structure (B) having a reactive group. In addition, the crosslinking agent preferably has a reactive group capable of reacting with the reactive group. Hereinafter, this polymer is sometimes referred to as a "particular polymer".

[0037] < Unit structure (A) > The unit structure (A) is a unit structure having a polycyclic aromatic structure.

[0038] In the present specification, a polycyclic aromatic structure refers to a structure composed of 2 or more aromatic rings showing aromaticity, and includes a fused polycyclic aromatic structure having a fused ring, and an aromatic ring collection structure in which a plurality of aromatic rings are directly bonded by a single bond.

[0039] The polycyclic aromatic structure can be a structure composed only of hydrocarbons, or a structure having a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom).

[0040] As the fused polycyclic aromatic structure, there is no particular limitation, and examples include a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a triphenylene structure, a chrysene structure, a tetracene structure, a biphenalene structure, and a fluorene structure.

[0041] As the aromatic ring collection structure, there is no particular limitation, and examples include a carbazole structure, a biphenyl structure, a terphenyl structure, a quaterphenyl structure, a binaphthyl structure, a phenylnaphthyl structure, a phenylfluorenyl structure, and a diphenylfluorenyl structure.

[0042] The polycyclic aromatic structure is preferably selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, tetracene, biphenalene, fluorene, and carbazole, each of which can be substituted.

[0043] The polycyclic aromatic structure (fused polycyclic aromatic structure, aromatic ring collection structure) can be substituted with a substituent. As the substituent that can be substituted, there is no particular limitation, and examples include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxyl group, an amino group, an amide group, an alkoxycarbonyl group, a thioalkyl group, and the like.

[0044] As the halogen atom, examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0045] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl It includes 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc. Furthermore, cyclic alkyl groups can also be used as the aforementioned alkyl groups. Examples of cyclic alkyl groups with 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-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-Dimethylcyclobutyl, 2,2-Dimethylcyclobutyl, 2,3-Dimethylcyclobutyl, 2,4-Dimethylcyclobutyl, 3,3-Dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl, etc.

[0046] Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, and isopropoxy.

[0047] Examples of amide groups with 1 to 12 carbon atoms include: formamido, acetamido, propionamido, isobutyramido, benzamide, naphthamido, acrylamide, etc.

[0048] Examples of alkoxycarbonyl groups include those with 2 to 12 carbon atoms. Examples of alkoxycarbonyl groups with 2 to 12 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl.

[0049] As the alkylthio group, for example, an alkylthio group having 1 to 6 carbon atoms can be given. As the alkylthio group having 1 to 6 carbon atoms, for example, methylthio group, ethylthio group, butylthio group, hexylthio group, and the like can be given.

[0050] From the viewpoint of appropriately obtaining the effects of the present application, the polycyclic aromatic structure is preferably a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a triphenylene structure, a chrysene structure, a tetracene structure, a biphenalene 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 further preferably a naphthalene structure or a carbazole structure.

[0051] The polycyclic aromatic structure can be one or two or more, and is preferably one or two.

[0052] As the unit structure (A), there is no particular limitation, and from the viewpoint of appropriately obtaining the effects of the present application, a unit structure represented by the following formula (A-1) is preferred.

[0053] [Chemical Formula 7] ; (In formula (A-1), R 1 represents a hydrogen atom or a methyl group. X 1 represents a single bond, an ester group, or an amide group. Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms. Ar represents a monovalent group obtained by removing a hydrogen atom from a naphthalene, an anthracene, a phenanthrene, a pyrene, a triphenylene, a chrysene, a tetracene, a biphenalene, a fluorene, or a carbazole which can be substituted.) The unit structure represented by formula (A-1) includes a vinyl naphthalene having a naphthalene as Ar in the side chain, and the like.

[0054] As the substituent group which Ar can have, for example, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxyl group, an amino group, an amide group, an alkoxycarbonyl group, an alkylthio group, and the like can be given.

[0055] As the unit structure represented by formula (A-1), there is no particular limitation, and from the viewpoint of appropriately obtaining the effects of the present application, a unit structure represented by the following formula (A-1-1) is preferred.

[0056] [Chemical Formula 8] ; (In formula (A-1-1), R 1 represents a hydrogen atom or a methyl group. R 2 represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxyl group, an amino group, an amide group, an alkoxycarbonyl group, or an alkylthio group. n represents an integer of 0 to 7. When R 2 is two or more, the two or more R 2They can be the same or different. As the unit structure represented by formula (A-1), the following unit structures, for example, can be given.

[0057] [Chemical Formula 9]

[0058] [Chemical Formula 10] ;

[0059] The unit structure (A) in the specific polymer can be one or two or more, and is preferably one or two.

[0060] << Unit Structure (B) >> The unit structure (B) is a unit structure having a reactive group.

[0061] The unit structure (B) is a structure different from the unit structure (A). For example, the unit structure (B) does not have a polycyclic aromatic structure.

[0062] As the reactive group possessed by the unit structure (B), there is no particular limitation, and the following, for example, can be given: a hydroxyl group, an epoxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxyl 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, and an allyl group, and the like.

[0063] As the unit structure (B), there is no particular limitation, and from the viewpoint of appropriately obtaining the effects of the present application, at least either one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2) is preferred.

[0064] [Chemical Formula 11] ; (In formula (B-1), R 11 represents a hydrogen atom or a methyl group. X 11 represents an ester group or an amide group. R 12 represents a monovalent group having a reactive group having 1 to 12 carbon atoms.

[0065] In formula (B-2), R 13 represents a monovalent group having a reactive group having 1 to 12 carbon atoms. As the monovalent group having a reactive group having 1 to 12 carbon atoms in R 12 and R 13 , the following, for example, can be given: a hydroxylalkyl group having 1 to 12 carbon atoms.

[0066] As the hydroxylalkyl group having 1 to 12 carbon atoms, the following, for example, can be given: a hydroxylalkyl group having 1 to 6 carbon atoms.

[0067] As the hydroxyalkyl group having 1 to 12 carbon atoms, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, a hydroxycyclohexyl group, a dihydroxycyclohexyl group, a 3-hydroxy-1-adamantyl group, and the like can be given.

[0068] The number of hydroxyl groups possessed by the hydroxyalkyl group having 1 to 12 carbon atoms can be 1 or more than 2.

[0069] As the unit structure represented by formula (B-1), for example, a unit structure represented by formula (B-1-1) shown below can be given.

[0070] [Chemical Formula 12] ; (In formula (B-1-1), R 11 and R 12 respectively mean the same as R 11 and R 12 in formula (B-1).) As the unit structure represented by formula (B-1), for example, the following unit structures can be given.

[0071] [Chemical Formula 13] ; As the unit structure represented by formula (B-2), for example, the following unit structures can be given.

[0072] [Chemical Formula 14] ; As the unit structure containing an epoxy group as a reactive group, a unit structure derived from a compound represented by general formulae (I) to (XVII) described in Japanese Patent Application Publication No. 2012-62365 can be given.

[0073] The unit structure (B) in the specific polymer can be one or two or more, and is preferably one or two.

[0074] << Unit Structure (C) >> The specific polymer can have a unit structure other than the unit structure (A) and the unit structure (B). As such a unit structure, from the viewpoint of appropriately obtaining the effects of the present application, it is preferable that at least any one unit structure (C) selected from a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) from a maleimide structure.

[0075] Note that the unit structure (C) is a unit structure different from the unit structure (A) and the unit structure (B).

[0076] For example, the unit structure (C) does not have a polycyclic aromatic structure and the reactive group that the unit structure (B) has.

[0077] As the monocyclic aromatic ring that the unit structure (C-1) has, an aromatic hydrocarbon ring or an aromatic heterocyclic ring can be given, and an aromatic hydrocarbon ring is preferred. As such an aromatic hydrocarbon ring, a benzene ring can be given.

[0078] As the unit structure (C), there is no particular limitation, and from the viewpoint of appropriately obtaining the effects of the present application, at least either one of a unit structure (C-1) represented by the following formula (C-1-1) and a unit structure (C-2) represented by the following formula (C-1-2) is preferred.

[0079] [Chemical Formula 15] ; (In the formula (C-1-1), R 21 represents a hydrogen atom or a methyl group. X 21 represents a single bond, an ester group, or an amide group. Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms. R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In the case where R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In the case where R 22 may be the same or different.

[0080] In the formula (C-1-2), R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which can be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which can be substituted with a halogen atom. As the unit structure represented by the formula (C-1-1), for example, a unit structure represented by the following formula (C-1-1-1) or a unit structure represented by the following formula (C-1-1-2) can be given.

[0081] [Chemical Formula 16] ; (In the formula (C-1-1-1) and the formula (C-1-1-2), R 21 represents a hydrogen atom or a methyl group. Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms. R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In the case where R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. n represents an integer of 0 to 5. In the case where R 22 may be the same or different. In formula (C-1-1-2), n is preferably an integer of 1 to 5.

[0082] As the unit structure represented by formula (C-1-1), the following unit structures, for example, can be given.

[0083] [Chem. 17] ; As the unit structure represented by formula (C-1-2), the following unit structures, for example, can be given.

[0084] [Chem. 18] ; The unit structure (C) in the specific polymer can be one or two or more, and is preferably one or two.

[0085] The mole ratio of the unit structure (A) with respect to the total unit structures of the specific polymer is not particularly limited, and is preferably 40 mol% or more, more preferably 45 mol% or more, and particularly preferably 50 mol% or more from the viewpoint of appropriately obtaining the effects of the present application.

[0086] The mole ratio of the unit structure (A) with respect to the total unit structures of the specific polymer is preferably 95 mol% or less, more preferably 90 mol% or less, and particularly preferably 80 mol% or less.

[0087] In the case where the specific polymer has the unit structure (B), the mole ratio of the unit structure (B) with respect to the total unit structures of the specific polymer is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 15 mol% or more from the viewpoint of appropriately obtaining the effects of the present application.

[0088] The mole ratio of the unit structure (B) with respect to the total unit structures of the specific polymer is preferably 40 mol% or less, more preferably 35 mol% or less, and particularly preferably 30 mol% or less.

[0089] In the case where the specific polymer has the unit structure (C), the mole ratio of the unit structure (C) with respect to the total unit structures of the specific polymer is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 15 mol% or more from the viewpoint of appropriately obtaining the effects of the present application.

[0090] The mole ratio of the unit structure (C) with respect to the total unit structures of the specific polymer is preferably 40 mol% or less, more preferably 35 mol% or less, and particularly preferably 30 mol% or less.

[0091] The molar ratio of the unit structure (A) to the unit structure (B) (unit structure (A) / unit structure (B)) in the specific polymer is not particularly limited, and is preferably from 1 to 9, more preferably from 1.5 to 5.

[0092] The distribution of the unit structure in the specific polymer is not particularly limited. The specific polymer can be a block copolymer or a random copolymer.

[0093] The molecular weight of the specific polymer is not particularly limited, and the weight average molecular weight measured by gel permeation chromatography (hereinafter, sometimes abbreviated as GPC) is preferably from 1500 to 100000, more preferably from 2000 to 50000.

[0094] <Method for producing the specific polymer> The method for producing the specific polymer is not particularly limited, and for example, the specific polymer of the present embodiment can be obtained by reacting a carbon-carbon double bond possessed by a monomer providing the unit structure (A), a carbon-carbon double bond possessed by a monomer providing the unit structure (B), and a carbon-carbon double bond possessed by a monomer providing an arbitrary unit structure (C).

[0095] As the polymerization method of the specific polymer, known polymerization methods such as radical polymerization, anionic polymerization, cationic polymerization, and the like can be used. Various known techniques such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, and the like can be used.

[0096] The polymerization initiator used at the time of polymerization is not particularly limited, and for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[ (1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and 2,2'-azobis(2-methylpropyamidine) dihydrochloride, and the like can be used.

[0097] As the solvent used at the time of polymerization, there is no particular limitation, and for example, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, ethoxyacetic acid ethyl ester, hydroxyacetic acid ethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, pyruvic acid methyl ester, pyruvic acid ethyl ester, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like can be used. They can be used alone or in a mixture.

[0098] As the reaction temperature, there is no particular limitation, and for example, 20°C to 150°C can be mentioned.

[0099] As the reaction time, there is no particular limitation, and for example, 1 hour to 72 hours can be mentioned.

[0100] The solution containing the obtained polymer can also be directly used for the preparation of the resist underlayer film-forming composition. In addition, the polymer can also be recovered by precipitating and separating it in a poor solvent such as methanol, ethanol, isopropanol, water, or a mixed solvent thereof.

[0101] As the content of the specific polymer in the resist underlayer film-forming composition, there is no particular limitation, and from the viewpoint of solubility, it is preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 10% by mass, relative to the entire resist underlayer film-forming composition.

[0102] In addition, as the content of the specific polymer in the resist underlayer film-forming composition, it is preferably 50% by mass to 95% by mass, more preferably 55% by mass to 90% by mass, particularly preferably 60% by mass to 85% by mass, relative to the film-constituting components.

[0103] The film-constituting components refer to the components other than the solvent contained in the composition.

[0104] The resist underlayer film-forming composition contains a crosslinking agent.

[0105] The crosslinking agent preferably has a functional group capable of reacting with the reactive group possessed by the unit structure (B).

[0106] The number of the functional groups in the crosslinking agent is not particularly limited, and can be one or two or more.

[0107] ​As the functional group capable of reacting with the reactive group possessed by the unit structure (B), there is no particular limitation, and examples thereof include a hydroxyl group, an epoxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxyl 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, a structure represented by the following formula (D), and the like.

[0108] [Chemical Formula 19] ;

[0109] (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, a carbon atom constituting an aromatic hydrocarbon ring, or the like.

[0110] In the case where the reactive group possessed by the unit structure (B) is a hydroxyl group or a thiol group, as the functional group capable of reacting with the reactive group possessed by the unit structure (B), for example, a structure represented by the following formula (D) can be mentioned.

[0111] In the case where the reactive group possessed by the unit structure (B) is an epoxy group, as the functional group capable of reacting with the reactive group possessed by the unit structure (B), for example, a carboxyl group, an amino group, a thiol group, and the like can be mentioned.

[0112] As the crosslinking agent, a compound having two or more structures represented by the above formula (D) can be mentioned.

[0113] As R 101 , a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure is preferable.

[0114] [Chemical Formula 20] ;

[0115] (R 102 represents a hydrogen atom, a methyl group, or an ethyl group. represents a bond. As the crosslinking agent, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, and a compound having a phenolic hydroxyl group are preferable. They can be used alone or in combination of two or more.

[0116] As the melamine compound, there is no particular limitation as long as it is a melamine compound having a group capable of reacting with the reactive group (for example, a hydroxyl group) possessed by the unit structure (B).

[0117] As the melamine compound, for example, hexahydroxymethyl melamine, hexamethoxymethyl melamine, a compound or mixture thereof in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine are methoxymethylated, hexamethoxyethyl melamine, hexacyanoethyl melamine, a compound or mixture thereof in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine are acyloxymethylated, and the like can be given.

[0118] As the guanamine compound, there is no particular limitation as long as it is a guanamine compound having a group capable of reacting with the reactive group (e.g., hydroxyl group) possessed by the unit structure (B).

[0119] As the guanamine compound, for example, tetrahydroxymethyl guanamine, tetramethoxymethyl guanamine, a compound or mixture thereof in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, a compound or mixture thereof in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are acyloxymethylated, and the like can be given.

[0120] As the guanamine compound, there is no particular limitation as long as it is a guanamine compound having a group capable of reacting with the reactive group (e.g., hydroxyl group) possessed by the unit structure (B).

[0121] As the guanamine compound, for example, tetrahydroxymethyl guanamine, tetramethoxymethyl guanamine, a compound or mixture thereof in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, a compound or mixture thereof in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are acyloxymethylated, and the like can be given.

[0122] In addition, as the guanamine compound, for example, a guanamine derivative represented by the following formula (1E) can be given.

[0123] [Chemical Formula 21] ;

[0124] (In formula (1E), each of the 4 R1independently represents a methyl group or an ethyl group, and each of R2and R3independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) As the guanamine derivative represented by the formula (1E), for example, a compound represented by the following formula (1E-1) to formula (1E-6) can be given.

[0125] [Chemical Formula 22] ;

[0126] The guanamine derivative represented by the formula (1E) is obtained, for example, by reacting a guanamine derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0127] [Chemical Formula 23] ;

[0128] (In formula (2E), R2and R3each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4each independently represents an alkyl group having 1 to 4 carbon atoms.) [Chemical Formula 24] ;

[0129] (In formula (3d), R1represents a methyl group or an ethyl group.) As the glycoluril derivative represented by the formula (2E), for example, compounds represented by the following formulae (2E-1) to (2E-4) can be given. Further, as the compound represented by the formula (3d), for example, compounds represented by the following formulae (3d-1) and (3d-2) can be given.

[0130] [Chemical Formula 25]

[0131] [Chemical Formula 26] ;

[0132] As the urea compound, there is no particular limitation as long as it is a urea compound having a group capable of reacting with the reactive group (for example, a hydroxyl group) possessed by the unit structure (B).

[0133] As the urea compound, for example, tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetramethylol urea, or a mixture thereof, tetramethoxyethyl urea, and the like can be given.

[0134] As the compound having a phenolic hydroxyl group, for example, compounds represented by the following formula (111) or formula (112) can be given.

[0135] [Chemical Formula 27] ;

[0136] (In formulae (111) and (112), Q 2 represents a single bond or an organic group having a valence of m2.

[0137] R 8 , R 9 , R 11 , and R 12 each independently represent a hydrogen atom or a methyl group.

[0138] R 7 , and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms.

[0139] n9 represents an integer where 1 ≤ n9 ≤ 3, n 10 It means 2≤n 10 Integers ≤ 5, n 11 It means 0≤n 11 Integers ≤ 3, n 12 It means 0≤n 12 Integers ≤ 3, and 3 ≤ (n-9+n) 10 +n 11 +n 12 ≤6.

[0140] n 13 It means 1≤n 13 Integers ≤ 3, n 14 It means 1≤n 14 Integers ≤ 4, n 15 It means 0≤n 15 Integers ≤ 3, n 16 It means 0≤n 16 Integers ≤ 3, and 2 ≤ (n 13 +n 14 +n 15 +n 16 ≤5.

[0141] m2 represents an integer from 2 to 10. As Q 2 Organic groups with an m2 valence, for example, organic groups with an m2 valence having 1 to 4 carbon atoms.

[0142] Examples of compounds represented by formula (111) or formula (112) include the following compounds.

[0143] [Chemistry 28]

[0144] [Chemistry 29] ;

[0145] The aforementioned compound is available as a product of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, Asahi Organic Materials Co., Ltd.'s trade name TMOM-BP can be cited as a product.

[0146] Among them, glycourea compounds are preferred, specifically, tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, compounds or mixtures thereof obtained by acylmethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, with tetramethoxymethylglycourea being the most preferred.

[0147] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 500 or less.

[0148] The content of the crosslinking agent in the resist underlayer film-forming composition is not particularly limited, and is preferably 5 to 60 mass% of the specific polymer, more preferably 10 to 55 mass%, and particularly preferably 20 to 50 mass%.

[0149] < Curing Catalyst > The curing catalyst included as an arbitrary component in the resist underlayer film-forming composition can use any of thermal acid generators and photo acid generators, and preferably uses a thermal acid generator.

[0150] As the thermal acid generator, for example, sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium p-toluenesulfonate), phenolsulfonic acid pyridinium, p-hydroxybenzenesulfonic acid pyridinium (p-phenolsulfonic acid pyridinium), trifluoromethanesulfonic acid pyridinium, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, N-methylmorpholine-5-sulfosalicylic acid, and the like can be given.

[0151] As the photo acid generator, for example, onium salt compounds, sulfonimide compounds, and disulfonyl diazomethane compounds, and the like can be given.

[0152] As the onium salt compound, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and the like can be given. Further, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, and the like can be given.

[0153] As the sulfonimide compound, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalene dicarboxylic acid imide, and the like can be given.

[0154] As the disulfonyl diazomethane compound, for example, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(phenylsulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, and the like can be given.

[0155] The curing catalyst can use only one kind, or two or more kinds in combination.

[0156] When using a curing catalyst, the content of the curing catalyst relative to the crosslinking agent is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0157] <Other Ingredients> In the composition for forming the lower layer of the resist film, in order to further improve the coating performance on uneven surfaces and prevent the formation of pinholes, streaks, etc., a surfactant can be added.

[0158] Examples of surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl 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 nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. EFTOP Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Corporation, trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation, trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0159] There are no particular restrictions on the amount of these surfactants used, but they are typically 2.0% by mass or less, and preferably 1.0% by mass or less, relative to the composition for forming the underlayer film of the resist.

[0160] These surfactants can be added individually or in combination of two or more.

[0161] <Solvent> The composition for forming the resist underlayer film may contain a solvent.

[0162] As the solvent, organic solvents which are usually used for the liquid for the semiconductor lithography process are preferred. Specifically, the following can be mentioned: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, 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, gamma - butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0163] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0164] The content of the solvent in the composition for resist underlayer film formation is not particularly limited, and is preferably from 80 mass% to 99.99 mass%, more preferably from 90 mass% to 99.95 mass%, and particularly preferably from 95 mass% to 99.9 mass%.

[0165] <Substrate Containing Nitrogen Atom> The substrate on which the composition for resist underlayer film formation of the present application described above forms a film of a resist is a substrate containing a nitrogen atom.

[0166] The substrate containing a nitrogen atom can be mentioned, for example, a substrate containing a compound having a bond between a metal atom or a semi-metal atom and a nitrogen atom, or a substrate provided with a film containing a compound having a bond between a metal atom or a semi-metal atom and a nitrogen atom. The nitrogen atom can be contained in both the substrate and the film of the substrate.

[0167] The metal atom is not particularly limited, and can be mentioned, for example, titanium, gallium, tungsten, hafnium, zirconium, aluminum, copper, and the like. The semi-metal atom is not particularly limited, and can be mentioned, for example, boron, silicon, germanium, arsenic, antimony, tellurium, and the like.

[0168] As the substrate, for example, a silicon wafer, a germanium wafer, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, aluminum nitride, and the like can be mentioned. Among them, as the substrate containing a compound having a bond with a nitrogen atom, gallium nitride, indium nitride, aluminum nitride, and the like can be mentioned.

[0169] In addition, in the case where a film is formed on a substrate, as the film, for example, a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film formed by an ALD (Atomic Layer Deposition) method, a CVD (Chemical Vapor Deposition) method, a reactive sputtering method, an ion plating method, a vacuum evaporation method, or a spin coating method (spin on glass: SOG) can be given. Among them, as a nitrogen atom-containing film containing a compound having a bond with a nitrogen atom, for example, a silicon nitride film, a titanium nitride film, a titanium oxynitride film, a gallium nitride film, and the like can be given.

[0170] As an upper limit of the film thickness of the nitrogen atom-containing film, for example, 200 nm, 150 nm, 100 nm is given. As a lower limit, 5 nm, 10 nm is given.

[0171] Conventionally, when a resist film is formed on the above-described nitrogen atom-containing substrate, and light irradiation or electron beam irradiation is performed to obtain a resist pattern, the precision of the pattern is sometimes reduced. It is considered that the main reason is that an amine component from the nitrogen atom-containing substrate diffuses from the substrate side to the resist side in some processes. In contrast, in the case where the underlayer film is formed using the resist underlayer film-forming composition of the present application, the reduction in the precision of the above-described photoresist pattern can be suppressed.

[0172] (Underlayer film) The underlayer film (also referred to as a resist underlayer film) of the present application is a cured product of the above-described resist underlayer film-forming composition.

[0173] For the resist underlayer film, for example, it can be manufactured by applying the above-described resist underlayer film-forming composition to a nitrogen atom-containing substrate and performing baking.

[0174] Specifically, on a nitrogen atom-containing substrate, the resist underlayer film-forming composition of the present application is applied using a spin coater, a coater, or the like. Then, baking is performed using a hot plate or the like, whereby the underlayer film is formed. As the baking conditions, the baking temperature of 100°C to 400°C and the baking time of 0.3 minutes to 60 minutes can be appropriately selected. Preferably, the baking temperature is 120°C to 350°C, and the baking time is 0.5 minutes to 30 minutes, more preferably, the baking temperature is 150°C to 300°C, and the baking time is 0.8 minutes to 10 minutes.

[0175] As the film thickness of the underlayer film, for example, 0.001 mu m (1 nm) to 10 mu m, 0.002 mu m (2 nm) to 1 mu m, 0.005 mu m (5 nm) to 0.5 mum (500 nm), 0.001 mu m (1 nm) ~ 0.05 mu m (50 nm), 0.002 mu m (2 nm) ~ 0.05 mu m (50 nm), 0.003 mu m (3 nm) ~ 0.05 mu m (50 nm), 0.004 mu m (4 nm) ~ 0.05 mu m (50 nm), 0.005 mu m (5 nm) ~ 0.05 mu m (50 nm), 0.003 mu m (3 nm) ~ 0.03 mu m (30 nm), 0.003 mu m (3 nm) ~ 0.02 mu m (20 nm), 0.005 mu m (5 nm) ~ 0.02 mu m (20 nm), 0.005 mu m (5 nm) ~ 0.02 mu m (20 nm), 0.003 mu m (3 nm) ~ 0.01 mu m (10 nm), 0.005 mu m (5 nm) ~ 0.01 mu m (10 nm), 0.003 mu m (3 nm) ~ 0.006 mu m (6 nm), 0.003 mu m (3 nm) ~ 0.01 mu m (10 nm), or 0.005 mu m (5 nm).

[0176] The method for measuring the film thickness of the underlayer film in this specification is as shown below.

[0177] • Measuring device name: Ellipso film thickness measuring device RE-3100 (SCREEN Co., Ltd.) • SWE (single-wavelength ellipsometer) mode • Arithmetic mean of 8 points (for example, 8 points are measured at 1 cm intervals in the wafer X direction) (Method for manufacturing semiconductor element) The method for manufacturing a semiconductor element of the present application includes at least the following steps.

[0178] • A step of forming an underlayer film on a substrate containing a nitrogen atom using the resist underlayer film-forming composition of the present application, • a process of forming either of a photoresist film and an electron beam resist film on the underlayer film, • a process of performing light irradiation or electron beam irradiation on the resist film, followed by developing the resist film to obtain a resist pattern, and • a process of etching the underlayer film using the resist pattern as a mask to form a patterned underlayer film Generally, a resist film is formed on the underlayer film.

[0179] As the film thickness of the resist film, for example, 3000 nm or less, 2000 nm or less, 1800 nm or less, 1500 nm or less, 1000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, 10 nm.

[0180] As the resist film formed on the underlayer film by a known method (e.g., coating and baking of a resist composition), there is no particular limitation as long as it is a resist film that responds to light or an electron beam (EB) used in irradiation. Both a negative type photoresist and a positive type photoresist can be used.

[0181] Note that, in the present specification, a resist that responds to EB is also referred to as a photoresist.

[0182] As the photoresist, there are included: a positive type photoresist containing a Novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester; a chemically amplified photoresist containing a binder having a group that increases the alkali dissolution rate by decomposition under the action of an acid and a photo acid generator; a chemically amplified photoresist containing a low molecular compound that increases the alkali dissolution rate of the photoresist by decomposition under the action of an acid, an alkali-soluble binder, and a photo acid generator; and a chemically amplified photoresist containing a binder having a group that increases the alkali dissolution rate by decomposition under the action of an acid, a low molecular compound that increases the alkali dissolution rate of the photoresist by decomposition under the action of an acid, and a photo acid generator; a resist containing a metal element, and the like. For example, there are mentioned V146G manufactured by JSR Corporation, APEX-E manufactured by Shipley Company, PAR710 manufactured by Sumitomo Chemical Company, and AR2772, SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., and the like. In addition, there are mentioned, for example, fluorine atom-containing polymer-based photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000); Proc. SPIE, Vol. 3999, 357-364 (2000); Proc. SPIE, Vol. 3999, 365-374 (2000).

[0183] In addition, a so-called resist composition, metal-containing resist composition, and the like such as the resist composition, the radiation-sensitive resin composition, the high-resolution patterning composition based on an organic metal solution, and the like described in 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, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Patent Application Publication No. 2018-180525, WO2018 / 190088, Japanese Patent Application Publication No. 2018-070596, Japanese Patent Application Publication No. 2018-028090, Japanese Patent Application Publication No. 2016-153409, Japanese Patent Application Publication No. 2016-130240, Japanese Patent Application Publication No. 2016-108325, Japanese Patent Application Publication No. 2016-047920, Japanese Patent Application Publication No. 2016-035570, Japanese Patent Application Publication No. 2016-035567, Japanese Patent Application Publication No. 2016-035565, Japanese Patent Application Publication No. 2019-101417, Japanese Patent Application Publication No. 2019-117373, Japanese Patent Application Publication No. 2019-052294, Japanese Patent Application Publication No. 2019-008280, Japanese Patent Application Publication No. 2019-008279, Japanese Patent Application Publication No. 2019-003176, Japanese Patent Application Publication No. 2019-003175, Japanese Patent Application Publication No. 2018-197853, Japanese Patent Application Publication No. 2019-191298, Japanese Patent Application Publication No. 2019-061217, Japanese Patent Application Publication No. 2018-045152, Japanese Patent Application Publication No. 2018-022039, Japanese Patent Application Publication No. 2016-090441, Japanese Patent Application Publication No. 2015-10878, Japanese Patent Application Publication No. 2012-168279, Japanese Patent Application Publication No. 2012-022261, Japanese Patent Application Publication No. 2012-022258, Japanese Patent Application Publication No. 2011-043749, Japanese Patent Application Publication No. 2010-181857, Japanese Patent Application Publication No. 2010-128369, WO2018 / 031896, Japanese Patent Application Publication No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Publication No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Publication No. 2016-29498, Japanese Patent Application Publication No. 2011-253185, and the like can be used, but the present application is not limited to these.

[0184] As the resist composition, for example, the following composition can be mentioned.

[0185] An active light- or radiation-sensitive resin composition comprising a resin A having a repeating unit having an acid-decomposable group, a polar group of which is protected by a protecting group which can be detached by the action of an acid, and a compound represented by the following general formula (121).

[0186] [Chem. 30] ;

[0187] In the general formula (121), m represents an integer of 1 to 6.

[0188] R1and R2each independently represent a fluorine atom or a perfluoroalkyl group.

[0189] L1represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0190] L2represents an alkylene group which can have a substituent or a single bond.

[0191] W1represents a cyclic organic group which can have a substituent.

[0192] M + represents a cation.

[0193] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, which contains a compound having a metal-oxygen covalent bond and a solvent, the metal element constituting the above compound belonging to Groups 3 to 15 of the 3rd to 7th periods of the periodic table.

[0194] A radiation-sensitive resin composition containing a polymer having a first structural unit represented by the following formula (31) and a second structural unit containing an acid dissociable group represented by the following formula (32), and an acid generator.

[0195] [Chem. 31] ;

[0196] (In the formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. R 1 is a hydroxyl group, a sulphanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. In the case where n is 2 or more, a plurality of R 1 are the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In the formula (32), R 3A monovalent group having 1 to 20 carbon atoms containing the acid dissociable group described above. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A resist composition containing a resin (A1) and an acid generator, the 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.

[0197] [Chemical Formula 32] ;

[0198] [In the formula, R 2 represents an alkyl group having 1 to 6 carbon atoms which can have a halogen atom, a hydrogen atom, or a halogen atom, X 1 represents a single bond, , 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 can have one or more groups selected from a hydroxyl group and a carboxyl group. As the resist film, for example, the following resist films can be given.

[0199] A resist film containing a base resin containing a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit generating an acid bonded to a polymer main chain by exposure.

[0200] [Chemical Formula 33] ;

[0201] (In the formula (a1) and the formula (a2), R A each independently is a hydrogen atom or a methyl group. R 1 and R 2 each independently is a tertiary alkyl group having 4 to 6 carbon atoms. R 3 each independently is a fluorine atom or a methyl group. m is an integer of 0 to 4. X 1 is a single bond, a phenylene group, or a naphthylene group, or is a linking group having 1 to 12 carbon atoms containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. X 2 is a single bond, an ester bond, or an amide bond. As the resist material, for example, the following resist materials can be given.

[0202] A resist material containing a polymer having a repeating unit represented by the following formula (b1) or formula (b2).

[0203] [Chemical Formula 34] ;

[0204] (R1in formula (b1) and formula (b2) is a hydrogen atom or a methyl group. X A is a single bond or an ester group. X 1 is a single bond or an ester group. X 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, a part of methylene constituting the alkylene group can be replaced with an ether group, an ester group or a group containing a lactone ring, and at least one hydrogen atom contained in X 2 may be replaced with a bromine atom. X 3 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, a part of methylene constituting the alkylene group can be replaced with an ether group or an ester group. Rf 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. Furthermore, Rf 1 and Rf 2 may combine to form a carbonyl group. R 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, a part or all of the hydrogen atoms of these groups can be replaced with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amido group, a nitro group, a sultone group, a sulfo group or a group containing a sulfonium salt, a part of methylene constituting these groups can be replaced with an ether group, an ester group, a carbonyl group, a carbonate group or a sulfonate group. Furthermore, R 1 and R 2 may be bonded to form a ring together with the sulfur atom to which they are bonded.) A resist material comprising a base resin, the base resin comprising a polymer containing a repeating unit represented by the following formula (a).

[0205] [Chemical Formula 35] ;

[0206] (R1in formula (a) is a hydrogen atom or a methyl group. R A is a hydrogen atom or a methyl group. R 1 is a hydrogen atom or an acid-labile group. R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1is a single bond or a phenylene group, or is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which can contain an ester group or a lactone ring. X 2 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. Among them, m+u is an integer of 1 to 4. An antireflective composition which is an antireflective composition that generates an acid by exposure and changes the solubility in a developer by the action of the acid, The antireflective composition contains a base material component (A) which changes the solubility in a developer by the action of an acid, and a fluorine additive component (F) which exhibits a decomposability to an alkali developer, The fluorine additive component (F) contains a fluororesin component (F1) having a structural unit (f1) containing an alkali dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0207] [Chemical Formula 36] ;

[0208] [In the formula (f2-r-1), Rf 21 Each independently is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n" is an integer of 0 to 2. is a binding bond. The structural unit (f1) contains a structural unit represented by the following general formula (f1-1), or a structural unit represented by the following general formula (f1-2).

[0209] [Chemical Formula 37] ;

[0210] [In the formulae (f1-1), (f1-2), R each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable site. A aryl is a divalent aromatic cyclic group which can have a substituent. X 01 is a single bond or a divalent linking group. R 2 Each independently is an organic group having a fluorine atom. As a coating, a coating solution and a coating composition, for example, the following can be cited.

[0211] A coating comprising a metal oxo-hydroxo network having organic ligands through metal carbon bonds and / or metal carboxylate bonds.

[0212] Inorganic oxygen / hydroxyl group-based composition.

[0213] A coating solution comprising: an organic solvent, a first organometallic compound represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (wherein, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), a first organometallic compound represented by the formula R' n SnX 4-n (wherein, n = 1 or 2) or a mixture thereof, wherein R and R' are independently a hydrocarbon group having 1 to 31 carbon atoms, and X is a ligand having a hydrolytic bond to Sn or a combination thereof; and a hydrolytic metal compound represented by the formula MX' v (wherein, M is a metal selected from Groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand having a hydrolytic M-X bond or a combination thereof).

[0214] A coating solution comprising: an organic solvent, a first organometallic compound represented by the formula R (3 / 2-x / 2) (OH) x (wherein, 0 < x < 3) in an amount of about 0.0025 M to about 1.5 M of tin, R being an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, said alkyl group or cycloalkyl group being bonded to tin at a secondary or tertiary carbon atom.

[0215] An inorganic pattern forming precursor aqueous solution is a mixture comprising water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand comprising a peroxide group.

[0216] Irradiation of light or an electron beam is performed, for example, through a mask (reticle) for forming a prescribed pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. The resist underlayer film-forming composition of the present application is preferably used for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation applications, and more preferably for EUV (extreme ultraviolet) exposure applications.

[0217] The irradiation energy of the electron beam and the exposure amount of the light are not particularly limited.

[0218] Baking (PEB: Post Exposure Bake) is performed after irradiation of light or an electron beam and before development.

[0219] The baking temperature is not particularly limited, and is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0220] There is no particular limitation on the baking time, and it is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0221] For development, for example, an alkali developer is used.

[0222] As the developing temperature, for example, 5°C to 50°C can be given.

[0223] As the developing time, for example, 10 seconds to 300 seconds can be given.

[0224] As the alkali developer, for example, an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia; a primary amine such as ethylamine, n-propylamine; a secondary amine such as diethylamine, di-n-butylamine; a tertiary amine such as triethylamine, methyldiethylamine; an alcohol amine such as dimethyl ethanolamine, triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline; a cyclic amine such as pyrrole, piperidine; and the like can be used. In addition, an appropriate amount of an alcohol such as isopropyl alcohol, a surfactant such as a nonionic surfactant, and the like can be added to the above-described aqueous alkali solution and used. Among them, the preferred developer is an aqueous solution of a quaternary ammonium salt, and further preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Furthermore, a surfactant or the like can be added to these developers. A method in which an organic solvent such as butyl acetate is used instead of the alkali developer to develop the photoresist and the part of the photoresist which has not been improved in alkali solubility is developed can also be used.

[0225] Next, the formed resist pattern is used as a mask to etch the lower layer film. The etching can be dry etching or wet etching, and is preferably dry etching.

[0226] In the case where a film is formed on the surface of the substrate used, the surface of the film is exposed; in the case where no film is formed on the surface of the substrate used, the surface of the substrate is exposed. Then, by going through a process of processing the substrate by a publicly known method (dry etching method or the like), a semiconductor element can be manufactured.

[0227] Examples Hereinafter, examples will be given to specifically describe the content of the present application, but the present application is not limited to these examples.

[0228] The weight average molecular weight of the polymers shown in the following Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 of the present specification was determined by a gel permeation chromatography method (hereinafter, abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used in the determination, and the determination conditions and the like are shown below.

[0229] GPC column: TSKgel Super-Multipore HZ-N (2 pieces) Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation) <SYNTHESIS EXAMPLE 1> A solution of 2-vinylnaphthalene 5.68 g (molar ratio of 75% relative to the entire polymer 1), methyl methacrylate-2-hydroxyethyl ester 1.60 g (molar ratio of 25% relative to the entire polymer 1), and 2,2'-azobisisobutyronitrile 0.73 g was prepared in propylene glycol monomethyl ether acetate 32.00 g. After nitrogen substitution was performed on the reaction vessel, the solution was heated and stirred at 140°C for about 4 hours. The reaction solution was added dropwise to isopropyl alcohol, and the precipitate was recovered by suction filtration and dried under reduced pressure at 60°C to recover polymer 1. The weight average molecular weight Mw of the obtained polymer 1 was measured by GPC to be 8500. The structure present in polymer 1 is shown in the following formula.

[0230] [Chem. 38] ;

[0231] <SYNTHESIS EXAMPLE 2> A solution of 2-vinylnaphthalene 4.75 g (molar ratio of 55% relative to the entire polymer 2), benzyl methacrylate 2.96 g (molar ratio of 30% relative to the entire polymer 2), methyl methacrylate-2-hydroxypropyl ester 1.21 g (molar ratio of 15% relative to the entire polymer 2), and 2,2'-azobisisobutyronitrile 1.07 g was prepared in propylene glycol monomethyl ether acetate 40.00 g. After nitrogen substitution was performed on the reaction vessel, the solution was heated and stirred at 140°C for about 4 hours. The reaction solution was added dropwise to isopropyl alcohol, and the precipitate was recovered by suction filtration and dried under reduced pressure at 60°C to recover polymer 2. The weight average molecular weight Mw of the obtained polymer 2 was measured by GPC to be 5900. The structure present in polymer 2 is shown in the following formula.

[0232] [Chem. 39] ;

[0233] <SYNTHESIS EXAMPLE 3> A solution of 2-vinylnaphthalene 5.00 g (molar ratio of 55% relative to the entire polymer 3), methyl methacrylate-2-phenylethyl ester 2.91 g (molar ratio of 26% relative to the entire polymer 3), methyl methacrylate-2-hydroxypropyl ester 1.61 g (molar ratio of 19% relative to the entire polymer 3), and 2,2'-azobisisobutyronitrile 0.48 g was dissolved in propylene glycol monomethyl ether acetate 40.00 g. After nitrogen substitution of the reaction vessel, the solution was heated and stirred at 140°C for about 4 hours. The reaction solution was dropped into methanol, and the precipitate was recovered by suction filtration and dried under reduced pressure at 60°C to recover polymer 3. The weight average molecular weight Mw of the obtained polymer 3 was 6600 as measured by GPC in terms of polystyrene. The structure present in polymer 3 is shown in the following formula.

[0234] [Chem. 40] ;

[0235] <SYNTHESIS EXAMPLE 4> A solution of 2-vinylnaphthalene 2.94 g (molar ratio of 50% relative to the entire polymer 4), hydroxyethyl methacrylate 1.24 g (molar ratio of 25% relative to the entire polymer 4), N-cyclohexylmaleimide 1.71 g (molar ratio of 25% relative to the entire polymer 4), and 2,2'-azobisisobutyronitrile 0.12 g was dissolved in propylene glycol monomethyl ether acetate 24.00 g. After nitrogen substitution of the reaction vessel, the solution was heated and stirred at 140°C for about 4 hours. The reaction solution was dropped into isopropyl alcohol, and the precipitate was recovered by suction filtration and dried under reduced pressure at 60°C to recover polymer 4. The weight average molecular weight Mw of the obtained polymer 4 was 16300 as measured by GPC in terms of polystyrene. The structure present in polymer 4 is shown in the following formula.

[0236] [Chem. 41] ;

[0237] <SYNTHESIS EXAMPLE 5> A solution of 2-vinylnaphthalene 2.86 g (molar ratio of 50% relative to the entire polymer 5), N-cyclohexylmaleimide 1.68 g (molar ratio of 25% relative to the entire polymer 5), N-hydroxyethylmaleimide 1.32 g (molar ratio of 25% relative to the entire polymer 5), and 2,2'-azobisisobutyronitrile 0.12 g was dissolved in propylene glycol monomethyl ether acetate 24.00 g. After nitrogen substitution of the reaction vessel, the solution was heated and stirred at 140°C for about 4 hours. The reaction solution was dropped into isopropyl alcohol, and the precipitate was recovered by suction filtration and dried under reduced pressure at 60°C to recover polymer 5. The weight average molecular weight Mw of the obtained polymer 5 was 11900 as measured by GPC in terms of polystyrene. The structure present in polymer 5 is shown in the following formula.

[0238] [Chem. 42] ;

[0239] <SYNTHESIS EXAMPLE 6> Dissolve 2-vinylnaphthalene 7.22 g (molar ratio of 71% relative to the entire polymer 6), 4-tert-butylstyrene 0.50 g (molar ratio of 10% relative to the entire polymer 6), methyl 2-hydroxypropyl acrylate 1.80 g (molar ratio of 19% relative to the entire polymer 6), and 2,2'-azobisisobutyronitrile 0.48 g in propylene glycol monomethyl ether acetate 40.00 g. After nitrogen substitution of the reaction vessel, heat the solution and stir at 140°C for about 4 hours. Drop the reaction solution into methanol, recover the precipitate by suction filtration, and dry under reduced pressure at 60°C to recover polymer 6. The weight average molecular weight Mw of the obtained polymer 6 was 7300 as measured by GPC in terms of polystyrene. The structure present in polymer 6 is shown in the following formula.

[0240] [Chem. 43] ;

[0241] <COMPARATIVE SYNTHESIS EXAMPLE 1> Dissolve monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation) 100.00 g, 5,5-diethylbarbituric acid (manufactured by Rishin Chemical Corporation) 66.4 g, and benzyltriethylammonium chloride 4.1 g in propylene glycol monomethyl ether 682.00 g in a reaction vessel. After nitrogen substitution of the reaction vessel, react at 130°C for 24 hours to obtain a solution containing comparative polymer 1. Perform GPC analysis, and as a result, the weight average molecular weight of the obtained comparative polymer 1 was 6800 in terms of standard polystyrene. The structure present in comparative polymer 1 is shown in the following formula.

[0242] [Chem. 44] ;

[0243] (Preparation 1 of the composition for lower layer film formation) Mix the components in the proportions shown in Table 1, and filter using a polyethylene microfilter having a pore size of 0.05 mu μm, thereby respectively preparing the composition for lower layer film formation of Examples 1 to 6 and the composition for lower layer film formation of Comparative Example 1.

[0244] The abbreviations in Table 1 are as follows.

[0245] PyPTS: pyridinium p-toluenesulfonate PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetra(methoxymethyl)glycoluril (the following structural formula) [Chem. 45]

[0246] [Table 1]

[0247] (Anti-Resist Pattern Evaluation) <Formation of Underlayer Film> The underlayer film-forming compositions of Examples 1 to 6 and Comparative Example 1 were each applied to a nitrogen-containing substrate on which a 31.5 nm SiON film was formed, using a spin coater. The wafer was baked on a hot plate at 205 to 250°C for 60 seconds, and an underlayer film having a film thickness of 5 nm was obtained for each of Examples 1 to 6 and Comparative Example 1.

[0248] An underlayer film-coated wafer was produced by the same method as described above, and an underlayer film that had been stored in a clean room for 48 hours was produced.

[0249] <Formation Test of Resist Pattern Using ArF Scanner> An ArF resist solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SAIL X-206) was applied to the underlayer films of Examples 1 to 6 and Comparative Example 1 that had been stored in a clean room for the prescribed time, and a photoresist film having a film thickness of 100 nm was formed by baking at 85°C for 60 seconds. An NSR-S 307E scanner (wavelength 193 nm, NA = 0.85, σ = 0.93 / 0.85) manufactured by Nikon Corporation was used to perform exposure through a mask set so that the line width of the photoresist after development and the width between lines would be 0.1 mu m, that is, a dense line having a line width of 0.1 mu mu m and a line and space (L / S) = 1 / 1. Thereafter, the wafer was baked on a hot plate at 95°C for 60 seconds, and after cooling, development was performed using butyl acetate for 60 seconds, and a negative pattern was formed on the underlayer film of the resist.

[0250] For the obtained photoresist pattern, the underlayer film-coated wafer was stored in a clean room without being subjected to the formation of a photoresist film, and then the line width / pitch (L / S = 1 / 1) of the photoresist pattern after exposure and development was observed. In addition, the photoresist film was formed on the underlayer film of the underlayer film-coated wafer which had been stored in a clean room for 48 hours by the same method, and then the line width of the photoresist pattern after exposure and development was confirmed. The above exposure was performed at the optimum irradiation energy in each example. The pattern size was confirmed by a scanning electron microscope (Hitachi High-Technologies Corporation, CG4100), and the results of the amount of change in the pattern size after storage in a clean room for 48 hours (after 48 hours) and the pattern size continuously measured until exposure (after 0 hours) are shown in Table 2.

[0251] [Table 2]

[0252] In Examples 1 to 6, the amount of change in the pattern size was smaller in the case where the underlayer film-coated wafer was stored for 48 hours, as compared with Comparative Example 1. Thus, in each of the examples, it is considered that the amount of change in the pattern size is small because the diffusion of the amine component from the substrate having a film of SiON, SiN, TiN, or the like is blocked. In addition, it is considered that in each of the examples, the damage due to the diffusion of the above amine component is suppressed even when a few days elapse after the application of the underlayer film, and the change in the pattern size is suppressed. Therefore, the resist underlayer film-forming composition of the present embodiment is expected to be a material which can be widely used for coating applications involving a substrate containing a nitrogen atom, for a variety of semiconductor manufacturing processes.

Claims

1. A composition for forming a resist underlayer film, characterized in that, a polymer and a crosslinking agent, the polymer has a structural unit (A) having a polycyclic aromatic structure, The resist underlayer film forming composition is used in photolithography using a photoresist film or an electron beam resist film to form an underlayer film of the resist film on a substrate containing a nitrogen atom.

2. The resist underlayer film-forming composition according to claim 1, wherein The polymer has the polycyclic aromatic structure in a side chain of the polymer.

3. The composition for resist underlayer film formation according to claim 1, wherein The polycyclic aromatic structure is selected from the group consisting of unsubstituted or substituted naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenylene, fluorene, and carbazole.

4. The resist underlayer film-forming composition according to claim 1, wherein The unit structure (A) is a unit structure represented by the following formula (A-1), In formula (A-1), R 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond, an ester group or an amide group, Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms, and Ar represents a monovalent group obtained by removing a hydrogen atom from a naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenalene, fluorene or carbazole which is unsubstituted or substituted.

5. The resist underlayer film-forming composition according to claim 1, wherein The polymer further has a unit structure (B) having a reactive group, The crosslinking agent has a functional group capable of reacting with the reactive group.

6. The resist underlayer film-forming composition according to claim 5, wherein The unit structure (B) is at least one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2), In formula (B-1), R 11 represents a hydrogen atom or a methyl group, X 11 represents an ester group or an amide group, R 12 represents a monovalent group having 1 to 12 carbon atoms with the reactive group, In formula (B-2), R 13 represents a monovalent group having 1 to 12 carbon atoms with the reactive group.

7. The resist underlayer film-forming composition according to claim 1, wherein The polymer further has at least one unit structure (C) selected from the group consisting of a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) from a maleimide structure.

8. The resist underlayer film forming composition according to claim 7, wherein The unit structure (C-1) is a unit structure represented by the following formula (C-1-1), The unit structure (C-2) is a unit structure represented by the following formula (C-2-1), In formula (C-1-1), R 21 represents a hydrogen atom or a methyl group, X 21 represents a single bond, an ester group or an amide group, Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms, R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and n represents an integer of 0 to 5; in the case where R 22 is two or more, two or more R 22 are the same or different, In formula (C-1-2), R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom.

9. The resist underlayer film-forming composition according to claim 1, wherein The mole ratio of the unit structure (A) with respect to the total unit structures of the polymer is 40 mol% or more.

10. The resist underlayer film-forming composition according to claim 5, wherein The mole ratio of the unit structure (B) with respect to the total unit structures of the polymer is 5 mol% to 40 mol%.

11. The resist underlayer film-forming composition according to claim 1, wherein The polymer further has a unit structure (B) having a reactive group, and at least one unit structure (C) selected from the group consisting of a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) from a maleimide structure, The crosslinking agent has a functional group capable of reacting with the reactive group, The unit structure (A) is a unit structure represented by the following formula (A-1), The unit structure (B) is at least one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2), The unit structure (C-1) is a unit structure represented by the following formula (C-1-1), The unit structure (C-2) is a unit structure represented by the following formula (C-2-1), The mole ratio of the unit structure (A) with respect to the total unit structures of the polymer is 40 mol% or more, The mole ratio of the unit structure (B) with respect to the total unit structures of the polymer is 5 mol% to 40 mol%, In formula (A-1), R 1 represents a hydrogen atom or a methyl group, X 1 represents a single bond, an ester group or an amide group, Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms, and Ar represents a monovalent group obtained by removing a hydrogen atom from a naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenalene, fluorene or carbazole which is unsubstituted or substituted. In formula (B-1), R 11 represents a hydrogen atom or a methyl group, X 11 represents an ester group or an amide group, R 12 represents a monovalent group having 1 to 6 carbon atoms with the reactive group, In formula (B-2), R 13 represents a monovalent group having 1 to 6 carbon atoms with the reactive group, In formula (C-1-1), R 21 represents a hydrogen atom or a methyl group, X 21 represents a single bond, an ester group or an amide group, Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms, R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and n represents an integer of 0 to 5; in the case where R 22 is two or more, two or more R 22 are the same or different, In formula (C-1-2), R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which is substituted or unsubstituted with a halogen atom.

12. The resist underlayer film-forming composition according to claim 1, wherein The content of the crosslinking agent is 20 mass% to 50 mass% of the polymer.

13. An underlayer film characterized by, is formed on the substrate containing a nitrogen atom using the resist underlayer film forming composition according to any one of claims 1 to 12.

14. The underfilm of claim 13, wherein, The film thickness of the underlayer film is less than 10 nm.

15. A method for manufacturing a substrate with a resist pattern, characterized by, comprising: a step of forming an underlayer film on the substrate containing a nitrogen atom using the resist underlayer film forming composition according to any one of claims 1 to 12, a process of forming any one of a photoresist film and an electron beam resist film on the underlayer film, and a process of subjecting the resist film to light irradiation or electron beam irradiation, followed by developing the resist film to obtain a resist pattern.

16. The method of manufacturing a substrate with a resist pattern according to claim 15, wherein, The production method includes a process of forming the resist film after 12 hours or more have passed after the underlayer film is formed.

17. A method of manufacturing a semiconductor element, characterized by, comprises: a process of forming an underlayer film on the nitrogen atom-containing substrate using the resist underlayer film-forming composition according to any one of claims 1 to 12, a process of forming any one of a photoresist film and an electron beam resist film on the underlayer film, a process of subjecting the resist film to light irradiation or electron beam irradiation, followed by developing the resist film to obtain a resist pattern, and a process of etching the underlayer film using the resist pattern as a mask to form a patterned underlayer film. a process of forming an underlayer film on the nitrogen atom-containing substrate using the resist underlayer film-forming composition according to any one of claims 1 to 12, a process of forming any one of a photoresist film and an electron beam resist film on the underlayer film, a process of subjecting the resist film to light irradiation or electron beam irradiation, followed by developing the resist film to obtain a resist pattern, and a process of etching the underlayer film using the resist pattern as a mask to form a patterned underlayer film.

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