Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film for EB or EUV lithography, which contains (A) a polymer containing a hydroxyl group, (B) a photoacid generator containing a hydroxyl group in a cation part, (C) a crosslinking agent capable of reacting with the hydroxyl group, and (D) a solvent.

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method. Background Art

[0002] In the manufacture of semiconductor devices, micro-machining has been carried out by using photolithography of resist compositions. The above-mentioned micro-machining is to form a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiate active light such as ultraviolet rays thereon via a mask pattern depicting a pattern of a device, develop, and use the obtained photoresist pattern as a protective film to etch the substrate, thereby forming a processing method of fine concave-convex corresponding to the above-mentioned photoresist pattern on the substrate surface. In recent years, the high integration of semiconductor devices has progressed, and the active light used has been used in addition to the i-rays (wavelength 365nm), KrF excimer lasers (wavelength 248nm), and ArF excimer lasers (wavelength 193nm). In the most advanced micro-machining, the practical application of EUV light (wavelength 13.5nm) or EB (electron beam) has been studied. Accompanied by this, the poor formation of resist patterns caused by the influence from semiconductor substrates, etc. has become a big problem. Therefore, in order to solve this problem, a method of setting a resist lower film between a resist and a semiconductor substrate has been widely studied.

[0003] Patent Document 1 discloses a composition for forming an underlayer film for lithography containing a naphthalene ring having a halogen atom. Patent Document 2 discloses a halogenated antireflective film. Patent Document 3 discloses a composition for forming an underlayer film for resists. Patent Document 4 discloses an antireflective coating composition for improving pattern collapse tolerance in negative tone development, the composition containing a polymer, a photoacid generator containing a crosslinkable group, a compound capable of crosslinking the polymer and the photoacid generator, a thermal acid generator, and an organic solvent.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2006 / 003850

[0007] Patent Document 2: Japanese Patent Application No. 2005-526270

[0008] Patent Document 3: International Publication No. 2020 / 111068

[0009] Patent Document 4: Japanese Patent Application Publication No. 2021-18429 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Examples of the properties required of the resist underlayer film include no mixing with the resist film formed on the upper layer (insolubility in the resist solvent).

[0012] In addition, as a property required of the resist underlayer film, for example, improvement of sensitivity of the resist film can be mentioned.

[0013] The present invention is proposed in view of the above situation, and its purpose is to provide a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a pattern forming method, which can form a resist underlayer film having excellent solvent resistance to a resist solvent and can improve the sensitivity of the resist film.

[0014] Means for solving problems

[0015] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following gist.

[0016] That is, the present invention includes the following aspects.

[0017] [1] A composition for forming a resist underlayer film for EB or EUV lithography, comprising: a polymer containing a hydroxyl group (A), a photoacid generator containing a hydroxyl group in a cation portion (B), a crosslinking agent (C) capable of reacting with the hydroxyl group, and a solvent (D).

[0018] [2] The composition for forming a resist underlayer film for EB or EUV lithography according to [1], wherein the polymer (A) is at least one of the following (i) to (iii),

[0019] (i) a polyaddition product of a polyfunctional epoxy compound and one or more selected from the group consisting of polyfunctional carboxylic acids, polyfunctional phenols, polyfunctional thiols, isocyanuric acids, and barbituric acids;

[0020] (ii) poly(meth)acrylates containing hydroxyl groups;

[0021] (iii) Addition condensation products of an aromatic compound containing a phenolic hydroxyl group, an aromatic amine or an electron-rich aromatic compound and an aldehyde compound or a carbonyl compound.

[0022] [3] The resist underlayer film forming composition for EB or EUV lithography according to [1] or [2], wherein the photoacid generator (B) is a photoacid generator represented by the following formula (1).

[0023]

[0024] [In formula (1), p represents an integer of 1≤p≤4.

[0025] m represents an integer of 1≤m≤3, n represents an integer of 0≤n≤2, and n+m=3.

[0026] A represents an optionally substituted benzene ring or an optionally substituted naphthalene ring.

[0027] R 1 It represents an alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group, or an optionally substituted naphthyl group.

[0028] X - Represents a monovalent anion.

[0029] When m is 2 or more, A-(OH)p may be the same or different.

[0030] When n is 2, R 1 Can be the same or different.]

[0031] [4] The resist underlayer film forming composition for EB or EUV lithography according to any one of [1] to [3], wherein the photoacid generator (B) is a photoacid generator represented by the following formula (1-1).

[0032]

[0033] (In formula (1-1), R 11 represents an alkyl group having 1 to 6 carbon atoms. 12 represents an alkyl group having 1 to 6 carbon atoms. n represents 0 or 1. p represents 1 or 2. X - represents a monovalent anion. )

[0034] [5] The composition for forming a resist underlayer film for EB or EUV lithography according to any one of [1] to [4], wherein the crosslinking agent (C) is at least one of a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, and a compound having a phenolic hydroxyl group.

[0035] [6] The resist underlayer film forming composition for EB or EUV lithography according to any one of [1] to [5], further comprising a catalyst (E) for the reaction between the crosslinking agent (C) and the hydroxyl group.

[0036] [7] A composition for forming a resist underlayer film, comprising: a polymer containing a hydroxyl group (A), a photoacid generator containing a hydroxyl group in a cationic portion (B), a crosslinking agent (C) capable of reacting with the hydroxyl group, and a solvent (D),

[0037] The photoacid generator (B) is a photoacid generator represented by the following formula (1-1).

[0038]

[0039] (In formula (1-1), R 11 represents an alkyl group having 1 to 6 carbon atoms. 12 represents an alkyl group having 1 to 6 carbon atoms. n represents 0 or 1. p represents 1 or 2. X - represents a monovalent anion. )

[0040] [8] The resist underlayer film-forming composition according to any one of [1] to [7], which is a resist underlayer film-forming composition for forming a resist underlayer film for a positive photoresist.

[0041] [9] A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to any one of [1] to [7].

[0042]

[10] A semiconductor processing substrate comprising:

[0043] Semiconductor substrates, and

[0044] [9] The resist underlayer film described.

[0045]

[11] A method for manufacturing a semiconductor device, comprising the following steps:

[0046] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as described in any one of [1] to [7]; and

[0047] A step of forming a resist film on the resist underlayer film.

[0048]

[12] A pattern forming method comprising the following steps:

[0049] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to [7];

[0050] forming a resist film on the resist underlayer film;

[0051] irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and

[0052] A step of etching the resist underlayer film using the resist pattern as a mask.

[0053] Effects of the Invention

[0054] According to the present invention, there can be provided a resist underlayer film-forming composition capable of forming a resist underlayer film having excellent solvent resistance to a resist solvent and capable of improving the sensitivity of the resist film, a resist underlayer film for EB or EUV lithography, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a pattern forming method. DETAILED DESCRIPTION

[0055] Hereinafter, the present invention will be described in detail. It should be noted that the description of the constituent elements described below is for exemplification to illustrate the present invention, and the present invention is not limited to these contents.

[0056] (Resist underlayer film forming composition)

[0057] The resist underlayer film-forming composition of the present invention comprises a hydroxyl group-containing polymer (A), a photoacid generator (B) containing a hydroxyl group in a cation portion, a crosslinking agent (C) reactive with the hydroxyl group, and a solvent (D).

[0058] Since the resist underlayer film-forming composition of the present invention comprises a polymer (A) containing a hydroxyl group, a photoacid generator (B) containing a hydroxyl group in the cationic part, and a crosslinking agent (C) capable of reacting with the hydroxyl group, the photoacid generator (B) is introduced into the crosslinked structure of the resist underlayer film. Therefore, even when the resist underlayer film contacts a resist solvent, the photoacid generator (B) is not easily eluted from the resist underlayer film. As a result, the resist underlayer film obtained from the resist underlayer film-forming composition of the present invention has excellent solvent resistance to the resist solvent.

[0059] Furthermore, since the photoacid generator (B) is introduced into the cross-linked structure of the resist underlayer film and the solvent resistance to the resist solvent is improved, even if the content of the photoacid generator (B) is increased, the solvent resistance to the resist solvent is not easily reduced. Therefore, the content of the photoacid generator (B) can be increased. As a result, the sensitivity of the resist film can be improved.

[0060] The resist underlayer film-forming composition of the present invention can be suitably used for a resist underlayer film-forming composition for EB or EUV lithography. It should be noted that, in EB or EUV lithography, since the resist underlayer film does not require an anti-reflection function, the resist underlayer film-forming composition for EB or EUV lithography has a different purpose and use from an anti-reflection composition (e.g., an anti-reflection coating composition).

[0061] Furthermore, the resist underlayer film-forming composition of the present invention is preferably a resist underlayer film-forming composition for forming a resist underlayer film for a positive photoresist.

[0062] <Hydroxyl-containing polymer (A)>

[0063] The hydroxyl group-containing polymer (A) (hereinafter sometimes referred to as polymer (A)) is not particularly limited as long as it has a hydroxyl group. Examples of the hydroxyl group include primary hydroxyl groups, secondary hydroxyl groups, tertiary hydroxyl groups, and phenolic hydroxyl groups.

[0064] The polymer (A) has, for example, a hydroxyl group bonded to a secondary or tertiary carbon atom.

[0065] The polymer (A) has, for example, three or more hydroxyl groups in the molecule.

[0066] The polymer (A) is preferably at least one of the following (i) to (iii).

[0067] (i) a polyaddition product (polymer (Ai)) of a polyfunctional epoxy compound and one or more selected from the group consisting of polyfunctional carboxylic acids, polyfunctional phenols, polyfunctional thiols, isocyanuric acids, and barbituric acids

[0068] (ii) Hydroxyl-containing poly(meth)acrylate (polymer (A-ii))

[0069] (iii) Addition condensation products of an aromatic compound containing a phenolic hydroxyl group, an aromatic amine or an electron-rich aromatic compound and an aldehyde compound or a carbonyl compound (polymer (A-iii))

[0070] <<(i) Polymer (Ai)>>

[0071] The polymer (Ai) is an addition polymerization product of a polyfunctional epoxy compound and one or more selected from the group consisting of polyfunctional carboxylic acids, polyfunctional phenols, polyfunctional thiols, isocyanuric acids, and barbituric acids.

[0072] The constituent components of the polymer (A-1) may contain components other than the polyfunctional epoxy compound, the polyfunctional carboxylic acid, the polyfunctional phenol, the polyfunctional thiol, the isocyanuric acids, and the barbituric acids.

[0073] <<<Multifunctional Epoxy Compounds>>>

[0074] The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups.

[0075] The number of epoxy groups in the polyfunctional epoxy compound is preferably 2 to 3, more preferably 2.

[0076] The polyfunctional epoxy compound does not have, for example, a carboxyl group, a phenolic hydroxyl group, a mercapto group, or an amino group (—NH—).

[0077] As the polyfunctional epoxy compound, a compound represented by the following formula (11) or a compound represented by the following formula (12) is preferred.

[0078]

[0079] (In formula (11), X1 represents a group represented by any one of the following formulae (11-1) to (11-4). Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (11-5). A1, A2, A3, A4, A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group.

[0080] In formula (12), Q1 represents a divalent organic group represented by any one of the following formulae (12-1-1) to (12-1-4). n1 and n2 each independently represent 0 or 1. 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. )

[0081]

[0082] (In formulas (11-1) to (11-3), R1 to R5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may combine with each other to form a ring having 3 to 6 carbon atoms. R3 and R4 may combine with each other to form a ring having 3 to 6 carbon atoms.

[0083] In the formula (11-4), Z3 represents a single bond or a divalent group represented by the following formula (11-5). A7, A8 and A9 each independently represent a hydrogen atom, a methyl group or an ethyl group.

[0084] * indicates a bonding bond.

[0085] *1 represents a bond to a carbon atom in formula (11). *2 represents a bond to a nitrogen atom in formula (11).

[0086]

[0087] (In formula (11-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to the nitrogen atom in formula (11) or formula (11-4). *4 represents a bond.)

[0088]

[0089] (In formulas (12-1-1) to (12-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bond.

[0090] In formula (12-1-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 21 When there are 2 or more, 2 or more R 21 It can be the same or different.

[0091] In formula (12-1-2), Z4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. 22 When there are 2 or more, 2 or more R 22 Can be the same or different. 23 When there are 2 or more, 2 or more R 23 It can be the same or different.

[0092] In formula (12-1-3), n14 represents an integer of 0 to 4. 24 When there are 2 or more, 2 or more R 24 It can be the same or different.

[0093] In formula (12-1-4), Z5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. 25 When there are 2 or more, 2 or more R 25 Can be the same or different. 26 When there are 2 or more, 2 or more R 26 Can be the same or different.)

[0094] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0095] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic chain. Examples of the straight chain or branched chain alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, etc. Examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0096] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, an isopropoxy group, and the like.

[0097] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0098] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.

[0099] In the present specification, examples of the alkynyl group include groups in which the double bond of the alkenyl group exemplified in the above-mentioned "alkenyl group" is replaced with a triple bond.

[0100] In the present specification, examples of the alkenyloxy group include vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, and prenyloxy.

[0101] In the present specification, examples of the alkynyloxy group include a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a 2-methyl-2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

[0102] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0103] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0104] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group and the like.

[0105] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0106] In the present specification, examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.

[0107] Examples of the compound represented by formula (11) include the following compounds.

[0108]

[0109]

[0110] Examples of the compound represented by formula (12) include the following compounds.

[0111]

[0112] Examples of other polyfunctional epoxy compounds include 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-dihydroxymethylperfluorohexane diglycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, dicyclopentadienyl dimethanol diglycidyl ether, and 2,6 - diglycidylphenyl=glycidyl=ether, 1,1,2,2-tetrakis(4-glycidyloxyphenyl)ethane, 1,1,3-tris(4-glycidyloxyphenyl)propane, bisphenol hexafluoroacetone diglycidyl ether, bis(2,3-epoxycyclopentyl)ether, 1,2-bis(3,4-epoxycyclohexylmethoxy)ethane, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl)methyl ester, 4,5-epoxy-2-methylcyclohexanecarboxylic acid 4,5-epoxy-2-methylcyclohexanemethyl ester, adipate bis(3,4-epoxycyclohexylmethyl)ester, 1,2-epoxy-4-(oxiranyl)cyclohexane, 4-(spiro[3,4-epoxycyclohexane-1,5'-[1,3]di alkyl]-2'-yl)-1,2-epoxycyclohexane, diglycidyl adipate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, N,N,N',N'-tetraglycidyl-m-phenylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 4,4'-methylenebis(N,N-diglycidylaniline), 2-(4,4-dimethylpentane-2-yl)-5,7,7-trimethyloctanoate 2,2-bis(glycidyloxymethyl)butyl ester, bisphenol A type epoxy resin , bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, alicyclic polyglycidyl ether type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, anthracene novolac type epoxy resin, biphenyl novolac type epoxy resin, xylylene novolac type epoxy resin, trisphenol methane novolac type epoxy resin, tetraphenol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, etc., but are not limited to them.

[0113] The molecular weight of the polyfunctional epoxy compound is not particularly limited, and examples thereof include 150 to 600.

[0114] The polyfunctional epoxy compound can be used alone or in combination of two or more.

[0115] <<<Polyfunctional carboxylic acid>>>

[0116] The polyfunctional carboxylic acid is not particularly limited as long as it is a compound having two or more carboxyl groups.

[0117] The number of carboxyl groups in the polyfunctional carboxylic acid is preferably 2 to 3, more preferably 2. A polyfunctional carboxylic acid having 2 carboxyl groups is also referred to as a dicarboxylic acid.

[0118] The polyfunctional carboxylic acid, for example, does not have an epoxy group.

[0119] As the polyfunctional carboxylic acid, a compound represented by the following formula (13) is preferred.

[0120]

[0121] (In formula (13), Y1 represents an organic group having 1 to 10 carbon atoms.)

[0122] As Y1, for example, a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and a sulfur atom may be mentioned. In this case, the number of oxygen atoms in Y1 may be 2 or more. In addition, the number of sulfur atoms in Y1 may be 2 or more, and two sulfur atoms in Y1 may be continuous.

[0123] Examples of the hydrocarbon group include an alkylene group. The alkylene group may be linear, branched, or cyclic.

[0124] Examples of the compound represented by formula (13) include the following compounds.

[0125]

[0126] Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic group-containing dicarboxylic acids, etc. Specific examples thereof are shown below, and in the following examples, they may overlap with the specific examples of the above formula (13).

[0127] Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

[0128] Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 3,4-bis(2-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid, 2,4-bis(2-hydroxyphenyl)-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, and the like.

[0129] Examples of the dicarboxylic acid containing an aromatic group include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, and the like. formic acid, 1,4'-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-diphenyl dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 4,4'-diphenyl methane dicarboxylic acid, 4,4'-diphenyl ethane dicarboxylic acid, 4,4'-diphenyl propane dicarboxylic acid, 4,4'-diphenyl hexafluoro propane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4 '-Stilbene dicarboxylic acid, 4,4'-(1,2-ethynyldiyl) dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, terephthalic acid, 3,3'-terephthalic acid, 4-carboxycinnamic acid, terephthalic acid, 3,3'-(4-4'-(methylenedi-p-phenylene)) dipropionic acid, 4,4'-(4,4'-(oxydiphenylene)) dipropionic acid, -p-phenylene)) dipropionic acid, 4,4'-(4,4'-(oxydi-p-phenylene)) dibutyric acid, (isopropylidene di-p-phenylenedioxy) dibutyric acid, bis(p-carboxyphenyl) dimethylsilane, 1,5-(9-oxofluorene) dicarboxylic acid, 3,4-furancarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5- Oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 6-pyridinedicarboxylic acid, and the like.

[0130] The molecular weight of the polyfunctional carboxylic acid is not particularly limited, and for example, 100 to 400 may be mentioned.

[0131] The polyfunctional carboxylic acid can be used alone or in combination of two or more.

[0132] <<<Multifunctional phenol>>>

[0133] The polyfunctional phenol is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups.

[0134] The aromatic hydrocarbon ring to which the phenolic hydroxyl group is bonded may be a benzene ring or a naphthalene ring.

[0135] The number of phenolic hydroxyl groups in the polyfunctional phenol is preferably 2 to 3, more preferably 2.

[0136] For example, the polyfunctional phenol does not have an epoxy group.

[0137] As the polyfunctional phenol, a compound represented by the following formula (14) is preferred.

[0138]

[0139] (In formula (14), R 31 and R 32 Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

[0140] Z 11 It represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0141] n21 and n22 each independently represent an integer of 0 to 4.

[0142] In R 31 When there are 2 or more, 2 or more R 31 Can be the same or different. 32 When there are 2 or more, 2 or more R 32 Can be the same or different.)

[0143] When an alkylene group having 1 to 6 carbon atoms is substituted with a halogen atom, the substitution may be partial or all.

[0144] Examples of the compound represented by formula (14) include the following compounds.

[0145]

[0146] The molecular weight of the polyfunctional phenol is not particularly limited, and is, for example, 150 to 400.

[0147] The polyfunctional phenols can be used alone or in combination of two or more.

[0148] <<<Multifunctional thiol>>>

[0149] The polyfunctional thiol is not particularly limited as long as it is a compound having two or more mercapto groups.

[0150] The number of mercapto groups in the polyfunctional thiol is preferably 2 to 3, more preferably 2.

[0151] The polyfunctional thiol does not have an epoxy group, for example.

[0152] As the polyfunctional thiol, a compound represented by the following formula (15) is preferred.

[0153] HS-Y2—SH (15)

[0154] (In formula (15), Y2 represents an organic group having 1 to 10 carbon atoms.)

[0155] Examples of Y2 include an alkylene group having a carbon number of 1 to 10. The alkylene group may be linear, branched, or cyclic.

[0156] Examples of the polyfunctional thiol include 1,2-ethanedithiol, 1,3-propanedithiol, bis(2-mercaptoethyl) ether, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and pentaerythritol tris(3-mercaptopropyl) ether. As the polyfunctional thiol compound, commercially available products can be used, for example, Calends MT (registered trademark) PE1, Calends MT NR1, Calends MT BD1, TPMB, TEMB (all manufactured by Showa Denko K.K.), and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (all manufactured by SC Organic Chemical Co., Ltd.).

[0157] The molecular weight of the polyfunctional thiol is not particularly limited, and for example, 80 to 400 may be mentioned.

[0158] The polyfunctional thiol can be used alone or in combination of two or more.

[0159] <<<Isocyanuric acid>>>

[0160] The isocyanuric acid is not particularly limited as long as it is a compound having an isocyanuric acid skeleton having two or more -NH- groups.

[0161] Isocyanuric acids, for example, do not have an epoxy group.

[0162] As the isocyanuric acid, a compound represented by the following formula (16) is preferred.

[0163]

[0164] (In formula (16), R A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. )

[0165] As R A The hydrocarbon group having 1 to 10 carbon atoms includes, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and the like.

[0166] As isocyanuric acids, for example, the following compounds can be mentioned.

[0167]

[0168] The molecular weight of the isocyanuric acid is not particularly limited, and examples thereof include 129 to 400.

[0169] The isocyanuric acids can be used alone or in combination of two or more.

[0170] <<<Barbituric Acids>>>

[0171] The barbituric acid is not particularly limited as long as it is a compound having a barbituric acid skeleton having two -NH- groups.

[0172] Barbituric acids, for example, do not have an epoxy group.

[0173] As the barbituric acid, a compound represented by the following formula (17) is preferred.

[0174]

[0175] (In formula (17), R B and R C Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0176] As R B and R C The hydrocarbon group having 1 to 10 carbon atoms includes, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the like.

[0177] Examples of the barbituric acids include the following compounds.

[0178]

[0179] The molecular weight of the barbituric acid is not particularly limited, and examples thereof include 128 to 400.

[0180] The barbituric acids can be used alone or in combination of two or more.

[0181] <<<Other components>>

[0182] As other constituent components of the polymer (Ai), for example, monocarboxylic acid may be mentioned.

[0183] The monocarboxylic acid is not particularly limited as long as it is a compound having one carboxyl group.

[0184] The monocarboxylic acid, for example, does not have an epoxy group.

[0185] Examples of the monocarboxylic acid include compounds represented by the following formula (18).

[0186]

[0187] (In formula (18), Z represents a monovalent organic group obtained by removing one hydrogen atom from the aliphatic ring which may be substituted with a substituent and in which the carbon-carbon bond may be interrupted by a heteroatom.)

[0188] Examples of the compound represented by the following formula (18) include the following compounds.

[0189]

[0190]

[0191] The molecular weight of the monocarboxylic acid is not particularly limited, and for example, 50 to 400 may be mentioned.

[0192] The monocarboxylic acid can be used alone or in combination of two or more.

[0193] The addition polymerization reaction for obtaining the polymer (Ai) can be carried out in the presence of a catalyst, for example, tetrabutyl bromide. , ethyltriphenylphosphine bromide That kind of season The amount of the catalyst used can be selected from a range of 0.1 to 10% by mass relative to the total mass of the polymer raw material used in the reaction. The temperature and time of the addition polymerization reaction can be selected from the range of 80 to 160° C. and 2 to 50 hours for the best conditions.

[0194] <<(ii) Polymer (A-ii)>>

[0195] The polymer (A-ii) is a poly(meth)acrylate containing a hydroxyl group.

[0196] The polymer (A-ii) has, for example, a structural unit represented by the following formula (21).

[0197]

[0198] (In formula (21), R 51 represents a hydrogen atom, a methyl group, or a halogen atom, Q 51 represents a single bond or a divalent connecting group, R 52 represents a monovalent organic group having a hydroxyl group. )

[0199] As Q 51 The divalent linking group in is not particularly limited, and examples thereof include -C(=O)O-, -O-, -C(=O)-N(-R)- (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -NHC(=O)NH-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-.

[0200] As R 52 The monovalent organic group having a hydroxyl group in is not particularly limited, and examples thereof include monovalent organic groups having 1 to 30 carbon atoms and having a hydroxyl group.

[0201] As R 52 Examples of the monovalent organic group having a hydroxyl group include an alkyl group having 1 to 10 carbon atoms and having a hydroxyl group, an aralkyl group having a hydroxyl group, a carbocyclic aromatic group having a hydroxyl group, and a heterocyclic aromatic group having a hydroxyl group.

[0202] The polymer (A-ii) is obtained, for example, by polymerizing a compound having a hydroxyl group and a polymerizable unsaturated group.

[0203] The polymer (A-ii) can be obtained, for example, by copolymerizing a compound having a hydroxyl group and a polymerizable unsaturated group with a compound having a polymerizable unsaturated group as another monomer.

[0204] The compound having a hydroxyl group and a polymerizable unsaturated group has, for example, one or more groups containing an ethylenically unsaturated group such as a (meth)acryloyl group, a vinylphenyl group, an acryl ether group, an allyl ether group, or a vinyl ether group, and one or more hydroxyl groups.

[0205] Note that the term "(meth)acryloyl" refers to acryloyl and / or methacryloyl, and similarly, the term "(meth)acrylic" refers to acrylic and / or methacrylic, and the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0206] As the group containing an ethylenically unsaturated group, preferably, a (meth)acryloyl group is used, and more preferably, an acryloyl group is used.

[0207] When the group containing an ethylenically unsaturated group is a (meth)acryloyl group, examples of the compound having a hydroxyl group and a polymerizable unsaturated group include hydroxyl group-containing (meth)acrylates.

[0208] Examples of the hydroxyl group-containing (meth)acrylate include monohydroxy mono(meth)acrylate having one hydroxyl group and one (meth)acryloyl group in one molecule, and polyhydroxy mono(meth)acrylate having a plurality of hydroxyl groups and one (meth)acryloyl group in one molecule.

[0209] Examples of the monohydroxymono(meth)acrylate include hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-phenoxypropyl(meth)acrylate, and 4-hydroxycyclohexyl(meth)acrylate; 3-chloro-2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxyalkyl(meth)acryloylphosphate; pentylene glycol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0210] Examples of the polyhydroxy mono(meth)acrylate include trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate.

[0211] Furthermore, when the group containing an ethylenically unsaturated group is a vinylphenyl group, examples of the compound having a hydroxyl group and a polymerizable unsaturated group include 4-vinylphenol, 2-hydroxyethyl-4-vinylphenyl ether, (2-hydroxypropyl)-4-vinylphenyl ether, (2,3-dihydroxypropyl)-4-vinylphenyl ether, and 4-(2-hydroxyethyl)styrene.

[0212] When the group containing an ethylenically unsaturated group is a propenyl ether group, examples of the compound having a hydroxyl group and a polymerizable unsaturated group include propenol, 2-hydroxyethyl propenyl ether, and 2,3-dihydroxypropyl propenyl ether.

[0213] When the group containing an ethylenically unsaturated group is an allyl ether group, examples of the compound having a hydroxyl group and a polymerizable unsaturated group include allyl alcohol, 2-hydroxyethyl allyl ether, and 2-hydroxypropyl allyl alcohol.

[0214] Furthermore, when the group containing an ethylenically unsaturated group is a vinyl ether group, examples of the compound having a hydroxyl group and a polymerizable unsaturated group include 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether.

[0215] These compounds having a hydroxyl group and a polymerizable unsaturated group may be used alone or in combination of two or more.

[0216] The compound having a polymerizable unsaturated group used for copolymerization with the compound having a hydroxyl group and a polymerizable unsaturated group is not particularly limited, and examples thereof include acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes.

[0217] Examples of the acrylic acid esters include substituted or unsubstituted alkyl acrylic acid esters in which the alkyl group has 1 to 10 carbon atoms, aralkyl acrylic acid esters, and aryl acrylic acid esters.

[0218] Examples of the methacrylic acid esters include substituted or unsubstituted alkyl methacrylates in which the alkyl group has 1 to 10 carbon atoms, aralkyl methacrylates, and aryl methacrylates.

[0219] Examples of the acrylamides include N-alkyl acrylamide, N-aryl acrylamide, N,N-dialkyl acrylamide, N,N-diaryl acrylamide, N-methyl-N-phenyl acrylamide, and N-2-acetamidoethyl-N-acetylacrylamide.

[0220] Examples of the methacrylamides include N-alkyl methacrylamide, N-aryl methacrylamide, N,N-dialkyl methacrylamide, N,N-diaryl methacrylamide, N-methyl-N-phenyl methacrylamide, and N-ethyl-N-phenyl methacrylamide.

[0221] Examples of the vinyl ethers include alkyl vinyl ethers and vinyl aryl ethers.

[0222] Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, and vinyl pivalate.

[0223] Examples of the styrenes include styrene, alkylstyrene, alkoxystyrene, halogenated styrene, carboxystyrene and the like.

[0224] <<(iii) Polymer (A-iii)>>

[0225] The polymer (A-iii) is an addition condensation product of an aromatic compound containing a phenolic hydroxyl group, an aromatic amine or an electron-rich aromatic compound and an aldehyde compound or a carbonyl compound. The addition condensation products of phenol or naphthol as an aromatic compound containing a phenolic hydroxyl group and an aldehyde compound or a carbonyl compound are known as phenol novolac and naphthol novolac, respectively, and these can also be used as the polymer (A-iii).

[0226] Examples of the aromatic compound containing a phenolic hydroxyl group include phenol, dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2′-biphenol, 1,4-bis[bis(4-hydroxyphenyl)methyl]benzene, and bisphenolfluorene.

[0227] Examples of the aromatic amine include aniline, diphenylamine, phenylnaphthylamine, hydroxydiphenylamine, phenylnaphthylamine, N,N'-diphenylethylenediamine, N,N'-diphenyl-1,4-phenylenediamine, and the like, and examples include aromatic amines containing phenolic hydroxyl groups on these aromatic rings. In the case of aromatic amines that do not contain phenolic hydroxyl groups on the aromatic ring, a polymer containing a hydroxyl group can be synthesized by addition condensation with an aldehyde compound or a carbonyl compound together with an aromatic compound containing a phenolic hydroxyl group.

[0228] Examples of the electron-rich aromatic compound include carbazole and indole, and examples of the electron-rich aromatic compound containing a phenolic hydroxyl group on the aromatic ring thereof. In the case of an electron-rich aromatic compound that does not contain a phenolic hydroxyl group on the aromatic ring, a polymer containing a hydroxyl group can be synthesized by performing addition condensation with an aldehyde compound or a carbonyl compound together with an aromatic compound containing a phenolic hydroxyl group.

[0229] The molecular weight of the polymer (A) is not particularly limited.

[0230] The weight average molecular weight of the polymer (A) is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

[0231] The content of the polymer (A) in the resist underlayer film-forming composition is not particularly limited, but is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the film constituent components.

[0232] <Photoacid generator (B)>

[0233] The photoacid generator (B) contains a hydroxyl group in the cation portion.

[0234] As the hydroxyl group, a phenolic hydroxyl group is preferred from the viewpoint of reactivity. The phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic hydrocarbon ring.

[0235] The number of hydroxyl groups in the photoacid generator (B) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 2, and particularly preferably 1.

[0236] As the cation part, a sulfonium cation is preferred.

[0237] As the photoacid generator (B), a photoacid generator represented by the following formula (1) is preferred.

[0238]

[0239] [In formula (1), p represents an integer of 1≤p≤4.

[0240] m represents an integer of 1≤m≤3, n represents an integer of 0≤n≤2, and n+m=3.

[0241] A represents an optionally substituted benzene ring or an optionally substituted naphthalene ring.

[0242] R 1 It represents an alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group, or an optionally substituted naphthyl group.

[0243] X - Represents a monovalent anion.

[0244] When m is 2 or more, A-(OH)p may be the same or different.

[0245] When n is 2, R 1 Can be the same or different.]

[0246] Preferably, m=1 and n=2, or m=3 and n=0.

[0247] As R 1 The substituent of the phenyl group which may be substituted and the naphthyl group which may be substituted includes, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0248] As R 1 , preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

[0249] As the photoacid generator (B), a photoacid generator represented by the following formula (1-1) is more preferred.

[0250]

[0251] (In formula (1-1), R 11represents an alkyl group having 1 to 6 carbon atoms. 12 represents an alkyl group having 1 to 6 carbon atoms. n represents 0 or 1. p represents 1 or 2. X - represents a monovalent anion. )

[0252] The monovalent anions in formula (1) and formula (1-1) are not particularly limited, and examples thereof include sulfonate anions, borate anions, antimonate anions, etc. Among them, sulfonate anions are preferred. Examples of sulfonate anions include non-fluorinated sulfonate anions, partially fluorinated sulfonate anions, and completely fluorinated sulfonate anions.

[0253] Examples of the sulfonate anion include anions represented by the following formula (X1).

[0254]

[0255] (In formula (X1), R 21 represents an alkyl group having 1 to 4 carbon atoms which may be partially or completely fluorinated.

[0256] As R 21 , preferably methyl or trifluoromethyl.

[0257] The content of the photoacid generator (B) in the resist underlayer film-forming composition is not particularly limited, but is, for example, 1 to 40% by mass, and preferably 5 to 25% by mass, based on the polymer (A).

[0258] <Crosslinking agent (C)>

[0259] The crosslinking agent (C) is not particularly limited as long as it can react with a hydroxyl group.

[0260] Examples of the cross-linking agent include compounds having two or more of the following structures.

[0261]

[0262] (In the structure, R 101 It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms.

[0263] * indicates a bond. )

[0264] The bonding bond is, for example, bonded to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0265] As R 101 , preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.

[0266]

[0267] (In the structure, R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond. )

[0268] As the crosslinking agent, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred, and these may be used alone or in combination of two or more.

[0269] The melamine compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0270] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

[0271] The guanamine compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0272] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

[0273] The glycoluril compound is not particularly limited as long as it is a glycoluril compound having a group reactive with a hydroxyl group.

[0274] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated or mixtures thereof, and the like.

[0275] In addition, the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).

[0276]

[0277] (In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0278] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0279]

[0280] The glycoluril derivative represented by the formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0281]

[0282] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0283]

[0284] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0285] Examples of the glycoluril derivative represented by the above formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4).

[0286] Further examples of the compound represented by the above formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0287]

[0288] The urea compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0289] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.

[0290] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (111) or formula (112).

[0291]

[0292] (In equations (111) and (112), Q 2 It represents a single bond or an m2-valent organic group.

[0293] R 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group.

[0294] R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0295] n9 represents an integer of 1≤n9≤3, n 10 It means 2≤n 10 An integer ≤5, n 11 Indicates 0≤n 11 An integer ≤3, n 12 Indicates 0≤n 12 Integer ≤3, 3≤(n9+n 10 +n 11 +n 12 )≤6.

[0296] n 13 Indicates 1≤n 13 An integer ≤3, n 14 Indicates 1≤n 14 An integer ≤ 4, n 15 Indicates 0≤n 15 An integer ≤3, n 16 Indicates 0≤n 16 Integer ≤3, 2≤(n 13 +n 14 +n 15 +n 16 )≤5.

[0297] m2 represents an integer from 2 to 10. )

[0298] As Q 2 The m2-valent organic group in includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0299] Examples of the compound represented by formula (111) or formula (112) include the following compounds.

[0300]

[0301] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. As the product, for example, TMOM-BP, a trade name of Asahi Organic Materials Industries, Ltd., can be mentioned.

[0302] Among them, glycoluril compounds are preferred, and specifically, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated or a mixture thereof, a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated or a mixture thereof are preferred, and tetramethoxymethyl glycoluril is preferred.

[0303] The molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 500 or less.

[0304] The content of the crosslinking agent (C) in the resist underlayer film-forming composition is not particularly limited, but is, for example, 1 mass % to 50 mass %, and preferably 5 mass % to 40 mass % based on the polymer (A).

[0305] <Solvent (D)>

[0306] As the solvent (D), an organic solvent generally used in a chemical solution for a semiconductor photolithography process is preferred. Specifically, 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, 2 ethyl-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0307] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0308] <Catalyst (E)>

[0309] As the catalyst (E) contained as an optional component in the resist underlayer film-forming composition, a thermal acid generator is preferably used.

[0310] The catalyst (E) is a catalyst for the reaction between the crosslinking agent (C) and the hydroxyl group.

[0311] Examples of the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine - p-Toluenesulfonate (pyridine -p-Toluenesulfonic acid), pyridine Phenolsulfonic acid, pyridine -p-Hydroxybenzenesulfonic acid (pyridinium phenolsulfonate Salt), pyridine - Sulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0312] The catalyst may be used alone or in combination of two or more.

[0313] When a catalyst is used, the content ratio of the catalyst is, for example, 0.1 mass % to 50 mass %, preferably 1 mass % to 30 mass % based on the cross-linking agent (C).

[0314] <Other ingredients>

[0315] A surfactant may be further added to the resist underlayer film-forming composition in order to prevent the generation of pinholes, streaks, and the like and to further improve the coating properties on uneven surfaces.

[0316] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate, Eftop EF301, EF303, EF352 (trade names of Tokem Projects), Megaphac F171, F173, R-30 (trade names of DIC Corporation), Fluoro FC430, FC 431 (manufactured by Sumitomo Slide Group, trade name), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc., organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0317] The amount of these surfactants blended is not particularly limited, but is usually 2.0 mass % or less, preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition.

[0318] These surfactants may be added alone or in combination of two or more.

[0319] The film constituting components contained in the resist underlayer film-forming composition, that is, the components other than the above-mentioned solvent, are, for example, 0.01% by mass to 10% by mass of the resist underlayer film-forming composition.

[0320] (Resist Underlayer Film)

[0321] The resist underlayer of the present invention is a cured product of the above-mentioned resist underlayer film-forming composition.

[0322] The resist underlayer film can be produced, for example, by applying the resist underlayer film-forming composition on a semiconductor substrate and firing the coating.

[0323] Examples of the semiconductor substrate to which the resist underlayer film-forming composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0324] When a semiconductor substrate having an inorganic film formed on the surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium oxide nitride film, tungsten film, gallium nitride film, and gallium arsenide film.

[0325] On such a semiconductor substrate, the resist lower film forming composition of the present invention is applied by a suitable coating method such as a spin coater or a coater. Then, a heating means such as a hot plate is used to bake to form a resist lower film. As baking conditions, it is appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0326] The thickness of the resist underlayer film is, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5 nm) to 0.05 μm (500 nm), and 0.006 μm (5 nm) to 0.05 μm (500 nm). 0nm), 0.003μm (3nm) ~ 0.03μm (30nm), 0.003μm (3nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.003μm (3nm) ~ 0.01μm (10nm), 0.005μm (5nm) ~ 0.01μm (10nm), 0.003μm (3nm) ~ 0.006μm (6nm), or 0.005μm (5nm).

[0327] The method for measuring the film thickness of the resist underlayer film in this specification is as follows.

[0328] ·Measurement device name: Ellipsometry film thickness measurement device RE-3100 (SCREEN Corporation)

[0329] SWE (Single Wavelength Ellipsometer) Mode

[0330] · Arithmetic average of 8 points (for example, 8 points are measured at 1 cm intervals along the X direction of the wafer)

[0331] (Substrates for semiconductor processing)

[0332] A semiconductor processing substrate of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.

[0333] As the semiconductor substrate, for example, the above-mentioned semiconductor substrates can be mentioned.

[0334] The resist underlayer film is disposed on, for example, a semiconductor substrate.

[0335] (Method for manufacturing semiconductor element, method for patterning)

[0336] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0337] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention; and

[0338] ・Step of forming a resist film on the resist underlayer film

[0339] The pattern forming method of the present invention includes at least the following steps.

[0340] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention;

[0341] A step of forming a resist film on the resist underlayer film;

[0342] · A step of irradiating the resist film with light or electron beams and then developing the resist film to obtain a resist pattern; and

[0343] A step of etching the resist underlayer film using the resist pattern as a mask.

[0344] Usually, a resist film is formed on the resist underlayer film.

[0345] The thickness of the resist film is preferably less than 200 nm, more preferably less than 150 nm, further more preferably less than 100 nm, and particularly preferably less than 80 nm. In addition, the thickness of the resist film is preferably more than 10 nm, more preferably more than 20 nm, and particularly preferably more than 30 nm.

[0346] The resist film formed on the resist underlayer film by a known method (eg, coating and firing) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative photoresists and positive photoresists can be used.

[0347] It should be noted that in this specification, a resist that responds to EB is also referred to as a photoresist.

[0348] As the photoresist, there are positive photoresists composed of novolac resin and 1,2-naphthoquinonediazosulfonate, chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases when decomposed by acid and a photoacid generator, chemically amplified photoresists composed of a low molecular weight compound whose alkali dissolution rate increases when decomposed by acid, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases when decomposed by acid, a low molecular weight compound whose alkali dissolution rate increases when decomposed by acid, and a photoacid generator, resists containing metal elements, and the like. For example, JSR Co., Ltd.'s product name V146G, Shipley Co., Ltd.'s product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430, etc. In addition, for example, fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be mentioned.

[0349] In addition, 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, W O2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japan Special opening 2016-035567, Japanese special opening 2016-035565, Japanese special opening 2019-101417, Japanese special opening 2019-117373, Japan Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019-06 1217. Japan Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 201 1-043749, Japanese Patent Application Laid-Open No. 2010-181857, Japanese Patent Application Laid-Open No. 2010-128369, WO2018 / 031896, Japanese Patent Application Laid-Open No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Laid-Open No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Laid-Open No. 2016-29498, Japanese Patent Application Laid-Open No. 2011-253185, etc., so-called resist compositions, metal-containing resist compositions, etc., but are not limited thereto.

[0350] As the resist composition, for example, the following compositions can be mentioned.

[0351] An active light-sensitive or radiation-sensitive resin composition comprising a resin A and a compound represented by the following general formula (121), wherein the resin A has a repeating unit having an acid-decomposable group in which a polar group is protected by a protecting group that is detached by the action of an acid.

[0352]

[0353] In the general formula (121), m represents an integer of 1-6.

[0354] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0355] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0356] L2 represents an alkylene group which may have a substituent or a single bond.

[0357] W1 represents a cyclic organic group which may have a substituent.

[0358] M + Represents a cation.

[0359] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the third to seventh periods of the third to fifteenth groups of the periodic table.

[0360] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) and containing an acid-dissociable group, and an acid generator.

[0361]

[0362] (In 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 thiol group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, a plurality of R 1 Same or different. 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 3 is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid dissociable group. Z is a single bond, an oxygen atom or a sulfur atom. 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. )

[0363] A resist composition comprising a resin (A1) comprising a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid-labile group, and an acid generator.

[0364]

[0365] [Wherein,

[0366] R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom, and X 1 Represents a single bond, -CO-O-* or -CO-NR 4 -*, * represents the bond with -Ar, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from a hydroxyl group and a carboxyl group.]

[0367] Examples of the resist film include the following.

[0368] A resist film comprises a base resin, wherein the base resin comprises a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit which generates an acid bonded to a polymer main chain upon exposure.

[0369]

[0370] (In formula (a1) and formula (a2), R A Each is independently a hydrogen atom or a methyl group. 1 and R 2 Each R is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each independently represents a fluorine atom or a methyl group. m represents an integer from 0 to 4. 1 X is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group and a naphthylene group. 2 is a single bond, an ester bond, or an amide bond. )

[0371] Examples of the resist material include the following.

[0372] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2).

[0373]

[0374] (In formula (b1) and formula (b2), R A X is a hydrogen atom or a methyl group. 1is a single bond or an ester group. 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a part of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring, and X 2 At least one hydrogen atom is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf 4 Each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 Can combine to form a carbonyl group. 1 ~R 5 Each is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and a part or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a group containing a sulfonium salt, and a part of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate group. In addition, R 1 With R 2 can combine to form a ring with the sulfur atom to which they are bound.)

[0375] A resist material includes a base resin, wherein the base resin includes a polymer containing a repeating unit represented by the following formula (a).

[0376]

[0377] (In formula (a), R A is a hydrogen atom or a methyl group. 1 is a hydrogen atom or an acid-labile group. 2 X is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 X is a single bond or a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. 2 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. Wherein, m+u is an integer of 1 to 4.)

[0378] A resist composition that generates acid upon exposure and changes its solubility in a developer by the action of the acid.

[0379] The invention comprises a base component (A) whose solubility in a developer changes due to the action of an acid and a fluorine additive component (F) which is decomposable by an alkaline developer.

[0380] 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).

[0381]

[0382] [In formula (f2-r-1), Rf 21 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n" is an integer from 0 to 2. * is a bonding bond.]

[0383] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0384]

[0385] [In formula (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable site. A aryl is a divalent aromatic cyclic group which may have a substituent. 01 is a single bond or a divalent linking group. 2 Each independently is an organic group having a fluorine atom.]

[0386] Examples of the coating material, coating solution, and coating composition include the following.

[0387] A coating comprises a metal oxy-hydroxy network having organic ligands via metal carbon bonds and / or metal carboxylate bonds.

[0388] Inorganic oxygen / hydroxyl based compositions.

[0389] A coating solution comprising: an organic solvent; a first organic metal composition having a formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (Here, 0<z≤2 and 0<(z+x)≤4), formula R' n S X 4-n(where n=1 or 2), or a mixture thereof, wherein R and R' are independently hydrocarbon groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; and a hydrolyzable metal compound represented by the formula MX' v (here, 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 hydrolyzable MX bond or a combination thereof).

[0390] A coating solution comprising an organic solvent and a formula RSnO (3 / 2-x / 2) (OH) x The coating solution of the first organometallic compound represented by (wherein 0<x<3) contains about 0.0025M to about 1.5M of tin in the above solution, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, and the above alkyl or cycloalkyl group is combined with tin on a secondary or tertiary carbon atom.

[0391] An aqueous precursor solution for forming an inorganic pattern comprises a mixture of water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group.

[0392] The irradiation of light or electron beams is carried out, for example, through a mask (photomask) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet rays) or EB (electron beams) are used. The resist underlayer film-forming composition of the present invention is preferably used for EB (electron beam) or EUV (extreme ultraviolet rays: 13.5 nm) irradiation, and more preferably used for EUV (extreme ultraviolet rays) exposure.

[0393] There are no particular restrictions on the irradiation energy of the electron beam and the exposure amount of light.

[0394] Baking (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beams and before development.

[0395] The baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0396] The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0397] In the development, for example, an alkaline developer is used.

[0398] As an image development temperature, 5 degreeC - 50 degreeC is mentioned, for example.

[0399] The development time may be, for example, 10 seconds to 300 seconds.

[0400] As alkaline developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, primary amines such as ethylamine, n-propylamine, secondary amines such as diethylamine, di-n-butylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, pyrrole, piperidine and other cyclic amines and other alkali aqueous solutions can be used. Further, it is also possible to add an appropriate amount of alcohols such as isopropanol, nonionic surfactants and the like to the aqueous solution of the above-mentioned alkalis and use them. Among them, the preferred developer is an aqueous solution of a quaternary ammonium salt, and more preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Further, surfactants and the like can also be added to these developers. It is also possible to use a method in which an organic solvent such as butyl acetate is used to develop the part of the photoresist where the alkali dissolution rate is not improved, instead of an alkaline developer.

[0401] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred.

[0402] When the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate is processed by a known method (dry etching method, etc.) to manufacture a semiconductor device.

[0403] Example

[0404] Next, the present invention will be specifically described with reference to synthesis examples and working examples, but the present invention is not limited thereto.

[0405] The weight average molecular weights of the polymers shown in the following Synthesis Examples 1 and 2 are the results of measurements obtained by gel permeation chromatography (hereinafter, abbreviated as GPC). The measurement was performed using a GPC apparatus manufactured by Tosoh Corporation, and the measurement conditions and the like were as follows.

[0406] Column temperature: 40°C

[0407] Flow rate: 0.35ml / min

[0408] Eluent: Tetrahydrofuran (THF)

[0409] Standard sample: Polystyrene (Tosoh Corporation)

[0410] <Synthesis example 1>

[0411] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.91 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 0.57 g of adamantane carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide were mixed. 0.14 g of (manufactured by ACROSS) was added to 6.87 g of propylene glycol monomethyl ether in a reaction container and dissolved. After the reaction container was replaced with nitrogen, it was reacted at 105°C for 8 hours to obtain a polymer solution. The polymer solution did not become turbid even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the result showed that the polymer in the obtained solution had a weight average molecular weight of 5000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a), (2a), and (3a).

[0412]

[0413] <Synthesis example 2>

[0414] 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.45 g of barbiturate (manufactured by Yashiro Pharmaceutical Co., Ltd.), and tetrabutyl bromide were mixed. 0.48 g was added to 56.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After the reaction vessel was purged with nitrogen, it was reacted for 10 hours by refluxing to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the resulting solution had a weight average molecular weight of 10,000 based on standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0415]

[0416] <Example 1>

[0417] To 0.038 g of the polymer obtained in Synthesis Example 1 above, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 0.004 g of 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate (product name: NDS-105, manufactured by Midori Chemical Co., Ltd.) (hereinafter referred to as PAG 1), 25.9 g of propylene glycol monomethyl ether and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0418]

[0419] <Example 2>

[0420] To 0.038 g of the polymer obtained in Synthesis Example 1 above, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 0.007 g of 4-hydroxy-1-naphthyl dimethylsulfonium trifluoromethanesulfonate (product name: NDS-105, manufactured by Midori Chemical Co., Ltd.) (hereinafter referred to as PAG 1), 25.9 g of propylene glycol monomethyl ether and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0421]

[0422] <Example 3>

[0423] To 0.038 g of the polymer obtained in Synthesis Example 2, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 0.007 g of 4-hydroxyphenyldimethylsulfonium methylsulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as PAG 2), 25.9 g of propylene glycol monomethyl ether and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0424]

[0425] <Comparative Example 1>

[0426] To 0.038 g of the polymer obtained in Synthesis Example 1 above, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 0.002 g of triphenylsulfonium trifluoromethanesulfonate (manufactured by Toyo Gosei Co., Ltd.) (hereinafter referred to as PAG 3), 25.9 g of propylene glycol monomethyl ether and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0427]

[0428] <Comparative Example 2>

[0429] To 0.038 g of the polymer obtained in Synthesis Example 1 above, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 0.004 g of triphenylsulfonium trifluoromethanesulfonate (manufactured by Toyo Gosei Co., Ltd.) (hereinafter referred to as PAG 3), 25.9 g of propylene glycol monomethyl ether and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0430]

[0431] <Comparative Example 3>

[0432] To 0.038 g of the polymer obtained in Synthesis Example 2, 0.01 g of tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments Co., Ltd.) and pyridine were added. 0.002 g of phenolsulfonic acid, 25.9 g of propylene glycol monomethyl ether, and 2.99 g of propylene glycol monomethyl ether acetate were dissolved, and then filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film-forming composition for lithography.

[0433] Table 1 summarizes the polymers and photoacid generators used in Examples 1 to 3 and Comparative Examples 1 to 3.

[0434] [Table 1]

[0435]

[0436] The addition amount in Table 1 indicates the addition amount (parts by mass) of the photoacid generator relative to 100 parts by mass of the polymer (phr; per hundred resin).

[0437] [Dissolution test of photoresist solvent]

[0438] The compositions for forming an anti-etching underlayer film of Example 1, Example 2, Example 3 and Comparative Examples 1, Comparative Examples 2, and Comparative Examples 3 were respectively applied on a silicon wafer as a semiconductor substrate by a spin coater. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form an anti-etching underlayer film (film thickness 5 nm). These anti-etching underlayer films were immersed in a mixed solvent of propylene glycol monomethyl ether (70 vol%) and propylene glycol monomethyl ether acetate (30 vol%) used as a solvent for the photoresist forming composition at room temperature for 1 minute, and then heated at 100°C for 30 seconds to remove the solvent, and then the film thickness was measured. The results of the solvent resistance test are shown in Table 2. When the film thickness reduction rate is 2% or less ( When the film thickness reduction rate was less than 2%, it was evaluated as "good", and when the film thickness reduction rate exceeded 2%, it was evaluated as "poor".

[0439] Film reduction rate (%) = [(A0-A1) / A0] × 100

[0440] A0: Film thickness before solvent resistance test

[0441] A1: Film thickness after solvent resistance test

[0442] [Table 2]

[0443] Example Solvent resistance test Example 1 good Example 2 good Example 3 good Comparative Example 1 good Comparative Example 2 bad Comparative Example 3 good

[0444] In Examples 1 to 3 in which PAG3 was added in an amount equal to or greater than that in Comparative Example 2, the solvent resistance was good. This confirmed that the solvent resistance was improved by using PAG1 and PAG2 as compared with PAG3.

[0445] [Formation of positive resist pattern using electron beam lithography apparatus]

[0446] The compositions for forming a resist underlayer film of Example 1 and Comparative Example 1 were respectively coated on a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. On the resist underlayer film, a positive resist solution for EUV (containing a methacrylic polymer) was spin-coated and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam drawing device (ELS-G130). After exposure, it was baked (PEB) at 100°C for 60 seconds, cooled on a cooling plate to room temperature, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with lines and spaces with a CD spacing of 30nm / 60nm. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi High Tech Novel Devices, CG4100). The results are shown in Table 3. In the formation of the above-mentioned resist pattern, the exposure required to obtain a pattern with a CD size of 30 nm is shown. The lower the number, the smaller the exposure amount is to obtain the target pattern.

[0447] [Table 3]

[0448]

[0449] It is found that in Example 1, the exposure amount required to obtain a pattern with a CD size of 30 nm can be reduced by about 11% compared to Comparative Example 1.

[0450] In addition, the compositions for forming the resist underlayer film of Example 3 and Comparative Example 3 were respectively coated on a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. On the resist underlayer film, a positive resist solution for EUV (containing a methacrylic polymer) was spin-coated and heated at 130°C for 60 seconds to form an EUV resist film. Using an electron beam drawing device (ELS-G130), the resist film was exposed under specified conditions. After exposure, it was baked (PEB) at 100°C for 60 seconds, cooled on a cooling plate to room temperature, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with lines and spaces with a CD spacing of 22nm / 44nm. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi High Tech Novel Devices, CG4100). The results are shown in Table 4. In the formation of the above-mentioned resist pattern, the exposure required to obtain a pattern with a CD size of 22 nm is shown. The lower the number, the smaller the exposure amount is to obtain the target pattern.

[0451] [Table 4]

[0452]

[0453] It is found that in Example 3, the exposure amount required to obtain a pattern with a CD size of 22 nm can be reduced by about 3% compared to Comparative Example 3.

Claims

1. A resist underlayer film-forming composition for EB or EUV lithography, comprising: a polymer containing a hydroxyl group (A), a photoacid generator containing a hydroxyl group in a cation portion (B), a crosslinking agent (C) capable of reacting with the hydroxyl group, and a solvent (D).

2. The resist underlayer film forming composition for EB or EUV lithography according to claim 1, wherein the polymer (A) is at least one of the following (i) to (iii), (i) a polyaddition product of a polyfunctional epoxy compound and one or more selected from the group consisting of polyfunctional carboxylic acids, polyfunctional phenols, polyfunctional thiols, isocyanuric acids, and barbituric acids; (ii) poly(meth)acrylates containing hydroxyl groups; (iii) Addition condensation products of an aromatic compound containing a phenolic hydroxyl group, an aromatic amine or an electron-rich aromatic compound and an aldehyde compound or a carbonyl compound.

3. The resist underlayer film forming composition for EB or EUV lithography according to claim 1, wherein the photoacid generator (B) is a photoacid generator represented by the following formula (1): In formula (1), p represents an integer of 1≤p≤4; m represents an integer of 1≤m≤3, n represents an integer of 0≤n≤2, and n+m=3; A represents a benzene ring which may be substituted or a naphthalene ring which may be substituted; R 1 represents an alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group, or an optionally substituted naphthyl group; X - represents a monovalent anion; When m is 2 or more, A-(OH)p may be the same or different; When n is 2, R 1 It can be the same or different.

4. The resist underlayer film forming composition for EB or EUV lithography according to claim 1, wherein the photoacid generator (B) is a photoacid generator represented by the following formula (1-1): In formula (1-1), R 11 represents an alkyl group having 1 to 6 carbon atoms; R 12 represents an alkyl group having 1 to 6 carbon atoms; n represents 0 or 1; p represents 1 or 2; X - Represents a monovalent anion. 5 . The resist underlayer film forming composition for EB or EUV lithography according to claim 1 , wherein the crosslinking agent (C) is at least one of a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, and a compound having a phenolic hydroxyl group. 6 . The composition for forming a resist underlayer film for EB or EUV lithography according to claim 1 , further comprising a catalyst (E) for the reaction between the crosslinking agent (C) and a hydroxyl group.

7. A resist underlayer film-forming composition comprising: a polymer containing a hydroxyl group (A), a photoacid generator containing a hydroxyl group in a cation portion (B), a crosslinking agent (C) capable of reacting with the hydroxyl group, and a solvent (D), The photoacid generator (B) is a photoacid generator represented by the following formula (1-1); In formula (1-1), R 11 represents an alkyl group having 1 to 6 carbon atoms; R 12 represents an alkyl group having 1 to 6 carbon atoms; n represents 0 or 1; p represents 1 or 2; X - Represents a monovalent anion. 8 . The resist underlayer film-forming composition according to claim 1 , which is a resist underlayer film-forming composition for forming a resist underlayer film for a positive photoresist. 9 . A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to claim 1 .

10. A semiconductor processing substrate comprising Semiconductor substrates, and The resist underlayer film according to claim 9.

11. A method for manufacturing a semiconductor device, comprising the following steps: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 7; and A step of forming a resist film on the resist underlayer film.

12. A pattern forming method comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 7; forming a resist film on the resist underlayer film; irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and A step of etching the resist underlayer film using the resist pattern as a mask.

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