Resist underlayer forming composition comprising an acid catalyst-supported polymer

Abstract

The present invention provides a composition for forming a resist sublayer capable of forming a desired resist pattern, a method for manufacturing a resist pattern using the resist sublayer forming composition, and a method for manufacturing a semiconductor device. The resist sublayer forming composition comprises a polymer having an acid compound supported at a terminal end and a solvent. The acid compound may ionicly bond with a base present at the polymer terminal end. The terminal end is, as shown in the following formula (1): It can be represented as (where A1 represents an acid compound, B represents a basic structure, and * is the binding site with a polymer residue).

Description

Technology Field

[0001] The present invention relates to a composition used in a lithography process in semiconductor manufacturing, particularly in state-of-the-art lithography processes (ArF, EUV, EB, etc.). Furthermore, the invention relates to a method for manufacturing a substrate with a resist pattern attached, to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device. Background Technology

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has been performed. This microfabrication is a processing method in which a thin film of a photoresist composition is formed on a semiconductor substrate, such as a silicon wafer, and active light such as ultraviolet rays is irradiated over it with a mask pattern having a device pattern drawn thereon, and then developed. The substrate is then etched using the resulting photoresist pattern as a protective film to form fine irregularities corresponding to the pattern on the surface of the substrate. Recently, as the integration density of semiconductor devices has increased, the active light used is also being considered for the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) for cutting-edge microfabrication, in addition to the conventionally used i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm). Consequently, defects in resist pattern formation caused by influence from the semiconductor substrate have become a major problem. Accordingly, to solve this problem, methods for providing a resist underlayer between the resist and the semiconductor substrate are being widely considered. Patent Document 1 discloses a resist underlayer forming composition for EUV lithography having a condensation polymer. Patent Document 2 discloses a resist underlayer forming composition comprising a polymer with alicyclic compound terminals. Prior art literature

[0003] International Patent Application Publication No. 2013 / 018802 International Patent Application Publication No. 2020 / 226141 The problem to be solved

[0004] Characteristics required for the resist underlayer include, for example, that intermixing with the resist film formed on the upper layer does not occur (it is insoluble in the resist solvent) and that the dry etching speed is faster than that of the resist film.

[0005] In the case of lithography involving EUV exposure, the line width of the formed resist pattern is 32 nm or less, and the resist underlayer for EUV exposure is formed with a thinner film thickness than conventionally. When forming such a thin film, pinholes and aggregation are prone to occur due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0006] Meanwhile, when forming a resist pattern, in the development process, a solvent capable of dissolving the resist film, usually an organic solvent, is used to remove the unexposed portion of the resist film and leave the exposed portion of the resist film as a resist pattern in a negative development process, or in a positive development process to remove the exposed portion of the resist film and leave the unexposed portion of the resist film as a resist pattern, improving the adhesion of the resist pattern is a major challenge.

[0007] The present invention aims to provide a composition for forming a resist sublayer capable of forming a desired resist pattern, which solves the above problem, and a method for forming a resist pattern using the resist sublayer forming composition. means of solving the problem

[0008] The present invention includes the following.

[0009] [1]

[0010] A resist underlayer forming composition comprising a polymer supporting an acid compound at its terminals and a solvent.

[0011] [2]

[0012] A resist underlayer forming composition described in [1], wherein the above acid compound is ionically bonded to a base present at the polymer end.

[0013] [3]

[0014] The above terminal is, the following formula (I):

[0015] [Chemical Formula 1]

[0016]

[0017] (In equation (I), A 1 A resist underlayer forming composition as described in [1] or [2], represented by (where B represents an acid compound, B represents a basic structure, and * is a binding site with a polymer residue).

[0018] [4]

[0019] The above B is a resist underlayer forming composition described in [3], which includes nitrogen atoms.

[0020] [5]

[0021] The above B is R 1 R 2 R 3 N and,

[0022] R 1 , and R 2 Each represents, independently, a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and

[0023] R 1 and R 2 It may form a ring with or without heteroatoms interposed, and

[0024] R 3 ... represents an aromatic group that may be substituted, or a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may be substituted, and

[0025] R 1 and R 2 When is not forming a ring, R 3is an aromatic group that may be substituted,

[0026] [3] or [4] A resist underlayer forming composition.

[0027] [6]

[0028] The above B,

[0029] [Chemical Formula 2]

[0030]

[0031] [During the meal,

[0032] R 1 , and R 2 Each represents, independently, a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and

[0033] R 3 represents an aromatic group that may be substituted.], or

[0034] The following formula (II)

[0035] [Chemical Formula 3]

[0036]

[0037] [Among Equation (II),

[0038] R is a hydrogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a combination thereof, and

[0039] R' is,

[0040] [Chemical Formula 4]

[0041]

[0042] And,

[0043] R a and R b Each represents an arbitrarily substituted alkyl group independently, and

[0044] X is O, S, or SO2, and

[0045] n and m are independently 2, 3, 4, 5, or 6, respectively.

[0046] A resist underlayer forming composition described in [3] or [4], which is a base represented by .

[0047] [7]

[0048] The above R 3 This represents a phenyl, naphthyl, anthracenyl, or phenanthrenyl group that may be substituted, and

[0049] The above R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group, and

[0050] The above R',

[0051] [Chemical Formula 5]

[0052]

[0053] A resist underlayer forming composition described in [6], which is a base represented by .

[0054] [8]

[0055] Above A 1 This, the following style

[0056] [Chemical Formula 6]

[0057]

[0058] A resist underlayer forming composition described in any one of [3] to [7], represented by (wherein A of formula (III) is a straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group that may be substituted, an aryl group that may be substituted by a group other than a carboxyl group, or a heteroaryl group that may be substituted).

[0059] [9]

[0060] The above polymer is, formula (1):

[0061] [Chemical Formula 7]

[0062]

[0063] [In the formulas, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 is formula (2), formula (3), formula (4), or formula (0):

[0064] [Chemical Formula 8]

[0065]

[0066] (In the formula, R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, and a phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 6 carbon atoms; additionally, R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, And, the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms), and Q represents Formula (5) or Formula (6):

[0067] [Chemical Formula 9]

[0068]

[0069] A polymer having a repeating unit structure represented by [wherein Q1 represents an alkylene group, a phenylene group, a naphthylene group, or anthrylene group having 1 to 10 carbon atoms, and the alkylene group, phenylene group, naphthylene group, and anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a combination thereof, and the alkylene group may be interrupted by a disulfide bond, n1 and n2 each represent a number of 0 or 1, and X2 represents formula (2), formula (3), or formula (0)] A resist underlayer forming composition described in any one of [1]~[8].

[0070]

[10]

[0071] A resist underlayer forming composition described in any one of [1] to [9], further comprising a crosslinking agent.

[0072]

[11]

[0073] A resist underlayer forming composition described in any one of [1] to

[10] , further comprising an acid-generating agent.

[0074]

[12]

[0075] [1]~

[11] A resist underlayer characterized by being a sintered product of a coating film formed from a resist underlayer forming composition described in any one of [1]~

[11] .

[0076]

[13]

[0077] A process of forming a resist underlayer by applying a resist underlayer forming composition described in any one of [1] to

[11] onto a semiconductor substrate and baking,

[0078] A process of forming a resist film by applying a resist onto the above-mentioned resist lower layer and baking,

[0079] A process of exposing the above-mentioned resist underlayer film and the semiconductor substrate coated with the above-mentioned resist,

[0080] A process of developing and patterning the above resist film after photolithography.

[0081] A method for manufacturing a patterned substrate comprising

[0082]

[14]

[0083] A process for forming a resist underlayer on a semiconductor substrate, comprising a resist underlayer forming composition described in any one of [1] to

[11] , and

[0084] A process of forming a resist film on the above-mentioned resist lower layer film, and

[0085] A process for forming a resist pattern by irradiating a resist film with light or electron beams and subsequent development, and

[0086] A process for forming a patterned resist lower layer by etching the resist lower layer through the formed resist pattern, and

[0087] Process of processing a semiconductor substrate using the patterned resist underlayer film.

[0088] A method for manufacturing a semiconductor device characterized by including Effects of the invention

[0089] The resist sublayer forming composition of the present invention has excellent coating properties on a semiconductor substrate to be processed, and excellent adhesion between the resist and the interface of the resist sublayer during resist pattern formation, thereby enabling the formation of a good resist pattern in the shape of a rectangle without peeling or collapse of the resist pattern. In particular, it exhibits a significant effect when using EUV (wavelength 13.5 nm) or EB (electron beam). Specific details for implementing the invention

[0090] <Resist Underlayer Forming Composition>

[0091] The resist underlayer forming composition of the present invention comprises a polymer having an acid compound supported at its terminals and a solvent.

[0092] Acid Compounds

[0093] The acid compound of the present invention is not limited to any acid compound that exhibits the effects of the present invention, and either a thermal acid generator or a photo-generating agent may be used. Examples of thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridinium salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxycyanoic acid.

[0094] Examples of the above photogenerative agents include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0095] Examples of onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0096] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormal butanesulfonyloxy)succinimide, N-(campersulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0097] Examples of disulfonyl diazomethane compounds include, for instance, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0098] The above acid compound may be used as a single type or in combination of two or more types.

[0099] There are no limitations on the method of supporting the above acid compound onto the polymer, but as described in the example, the acid compound can be supported by adding it to a polymer solution having a structure capable of supporting acid at the end and stirring. The ratio (mol%) of the acid compound supported on the polymer end can be indirectly calculated from the amount of acid compound removed during polymer purification by the manufacturing method described in the example, and it is preferable that the acid compound supported on the polymer end be, for example, 50 mol% or more, 70 mol% or more, 90 mol% or more, and 98 mol% or more.

[0100] The above acid compound also has the role of promoting the crosslinking reaction of the polymer with the crosslinking agent described below.

[0101] The above acid compound may be ionically bonded with a base present at the polymer end.

[0102] The above terminal is, the following formula (I):

[0103] [Chemical Formula 10]

[0104]

[0105] (In equation (I), A 1 It can be represented as follows: represents an acid compound, B represents a basic structure, and * is the binding site with a polymer residue.

[0106] The above B may include a nitrogen atom.

[0107] The above B is R 1 R 2 R 3 N and,

[0108] R 1 , and R 2 Each represents, independently, a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and

[0109] R 1 and R 2 It may form a ring with or without heteroatoms interposed, and

[0110] R 3 ... represents an aromatic group that may be substituted, or a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may be substituted, and

[0111] R 1 and R 2 When is not forming a ring, R 3 It can be an aromatic group that may be substituted.

[0112] The above B,

[0113] [Chemical Formula 11]

[0114]

[0115] [During the meal,

[0116] R 1 , and R 2 Each represents, independently, a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and

[0117] R 3 represents an aromatic group that may be substituted.], or

[0118] The following formula (II)

[0119] [Chemical Formula 12]

[0120]

[0121] [Among Equation (II),

[0122] R is a hydrogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a combination thereof, and

[0123] R' is,

[0124] [Chemical Formula 13]

[0125]

[0126] And,

[0127] R a and R b Each represents an arbitrarily substituted alkyl group independently, and

[0128] X is O, S, or SO2, and

[0129] n and m are independently 2, 3, 4, 5, or 6, respectively.

[0130] It can be a base represented by .

[0131] The above R 3 This represents a phenyl, naphthyl, anthracenyl, or phenanthrenyl group that may be substituted, and

[0132] The above R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group, and

[0133] The above R',

[0134] [Chemical Formula 14]

[0135]

[0136] It can be a base represented by .

[0137] Above A 1 This, the following style

[0138] [Chemical Formula 15]

[0139]

[0140] (In formula (III), A is a straight, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group that may be substituted, an aryl group that may be substituted by a group other than a carboxyl group, or a heteroaryl group that may be substituted.)

[0141] The above straight-chain, branched, or cyclic saturated aliphatic hydrocarbon groups include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, Examples include 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group.

[0142] Straight-chain, branched, or cyclic unsaturated aliphatic hydrocarbon groups include, for example, an ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethyl ethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propyl ethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group,1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, Examples include 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0143] Examples of aryl groups include, for instance, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthyl group, 2-anthyl group, 9-anthyl group, 1-phenanthyl group, 2-phenanthyl group, 3-phenanthyl group, 4-phenanthyl group, 9-phenanthyl group, etc.

[0144] Examples of heteroaryl groups include, for instance, furanyl group, thiophenyl group, pyrrolyl group, imidazolyl group, pyranyl group, pyridinyl group, pyrimidinyl group, pyrazinyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, quinuclideninyl group, indolyl group, furinyl group, quinolinyl group, isoquinolinyl group, chromenyl group, thiantrenyl group, phenothiazinyl group, phenoxazinyl group, xanthenyl group, acridinyl group, phenazinyl group, carbazolyl group, etc.

[0145] Aryl groups and heteroaryl groups are included in aromatic groups.

[0146] Examples of substituents include nitro groups, amino groups, cyano groups, sulfo groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, organic groups containing ether bonds, organic groups containing ketone bonds, organic groups containing ester bonds, or combinations thereof.

[0147] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0148] As for alkoxy groups, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, Examples include 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.

[0149] Regarding alkyl groups, alkenyl groups, and aryl groups, they are as exemplified above.

[0150] Organic groups containing ether bonds are R 11 -OR 11 (R 11 Each can be represented independently as an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group, and for example, an organic group including an ether bond including a methoxy group, an ethoxy group, or a phenoxy group can be cited.

[0151] Organic groups containing ketone bonds are R 21 -C(=O)-R 21 (R 21 Each can be represented independently as an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group, and examples include organic groups including ketone bonds such as an acetoxy group or a benzoyl group.

[0152] The organic group containing an ester bond is R 31 -C(=O)OR 31 (R 31 Each can be represented independently as an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group, and examples include organic groups containing ester bonds such as methyl esters, ethyl esters, and phenyl esters.

[0153] Meanwhile, A does not include an aryl group substituted by a hydroxyl group. Therefore, anions derived from p-phenolsulfonic acid, o-cresol-4-sulfonic acid, p-cresol-2-sulfonic acid, etc., are (A-SO3) in the present invention - It is not included in. Also, preferably, A does not include an aryl group substituted by a carboxyl group. Therefore, the anion derived from 5-sulfosalicylic acid, etc. is (A-SO3) in the present invention - It is not included in.

[0154] Preferably, A is a methyl group, a fluoromethyl group, or a tolyl group.

[0155] In the present invention, specific examples of B include N-methylmorpholine, N,N-diethylaniline, etc.

[0156] Polymer

[0157] The polymer included in the resist underlayer forming composition of the present invention is not limited to any polymer that exhibits the effects of the present invention, and is described in the following formula (1) as described in International Publication No. 2013 / 018802:

[0158] [Chemical Formula 16]

[0159]

[0160] [In the formulas, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 is formula (2), formula (3), formula (4), or formula (0):

[0161] [Chemical Formula 17]

[0162]

[0163] (In the formula, R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, and a phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 6 carbon atoms; additionally, R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, And, the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms), and Q represents Formula (5) or Formula (6):

[0164] [Chemical Formula 18]

[0165]

[0166] [In the formula, Q1 represents an alkylene group, a phenylene group, a naphthylene group, or anthrylene group having 1 to 10 carbon atoms, and the alkylene group, phenylene group, naphthylene group, and anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a combination thereof, and the alkylene group may be interrupted by a disulfide bond, n1 and n2 each represent a number of 0 or 1, and X2 represents formula (2), formula (3), or formula (0)].

[0167] Specific examples of the above alkyl group include methyl, ethyl, propyl, isopropyl, normal butyl, and cyclohexyl groups. Specific examples of the above alkenyl group include 2-propenyl and 3-butenyl groups. In addition, R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and examples of such rings include cyclobutane, cyclopentane, and cyclohexane rings.

[0168] Examples of the above alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, and isopropoxy groups.

[0169] The group having the disulfide group mentioned above may be a -SSR group or a -RSSR group. Here, R represents the aforementioned alkyl group, alkylene group, aryl group, and arylene group.

[0170] Specific examples of the repeating unit structure represented by Equation (1) include, for example, the repeating unit structures of Equations (13) to (32).

[0171] [Chemical Formula 19]

[0172]

[0173] [Chemical Formula 20]

[0174]

[0175] [Chemical Formula 21]

[0176]

[0177] [Chemical Formula 22]

[0178]

[0179] [Chemical Formula 23]

[0180]

[0181] In the above formula (32), R is an alcohol residue (an organic group other than the hydroxyl group of an alcohol), and this R represents an alkyl group, an ether group, or a combination thereof. Examples of the above R include alkyl groups, alkoxyalkyl groups, etc. Examples of alkyl groups and alkoxy groups can be given as described above.

[0182] The full disclosure of International Publication No. 2013 / 018802 is incorporated herein by reference.

[0183] The lower limit of the weight-average molecular weight of the polymer is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight-average molecular weight of the reaction product is, for example, 30,000, 20,000, or 10,000.

[0184] Solvent

[0185] The solvent used in the resist underlayer forming composition of the present invention is not particularly limited as long as it is a solvent capable of uniformly dissolving the solid contained components, such as the polymer, at room temperature, but an organic solvent generally used in chemicals for semiconductor lithography processes 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, 2-methyl isobutyrate, 2-ethyl isobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-ethyl ethoxypropionate, Examples include 3-methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactic acid, butyl lactic acid, 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.

[0186] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactic acid, butyl lactic acid, and cyclohexanone are preferred. In particular, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

[0187] Acid-generating agent

[0188] The acid-generating agent included as an optional component in the resist underlayer forming composition of the present invention may additionally include the same or different acid compound or acid-generating agent in addition to the acid compound supported on the polymer end. The acid-generating agent may be either a thermal acid-generating agent or a photo-generating agent, but it is preferable to use a thermal acid-generating agent. Examples of sulfonic acid compounds and carboxylic acid compounds include, for instance, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonic acid salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxycyanoic acid, etc.

[0189] Examples of the above photogenerative agents include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0190] Examples of onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0191] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormal butanesulfonyloxy)succinimide, N-(campersulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0192] Examples of disulfonyl diazomethane compounds include, for instance, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0193] The above acid-generating agent may be used as a single type or in combination of two or more types.

[0194] When the above acid-generating agent is used, the content ratio of the acid-generating agent is, for example, 0.1 mass% to 50 mass% with respect to the following crosslinking agent, and preferably 1 mass% to 30 mass%.

[0195] When the above acid-generating agent is used, the content ratio of the said acid-generating agent is 50 to 200 mol% and 80 to 150 mol% with respect to the polymer end.

[0196] <Cross-linking agent>

[0197] Examples of crosslinking agents included as optional components in the resist underlayer forming composition of the present invention include, for instance, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (tetramethoxymethylglycoluryl) (POWDERLINK [Registered Trademark] 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0198] In addition, the crosslinking agent of the present invention may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) that bond to a nitrogen atom, as described in International Publication No. 2017 / 187969.

[0199] [Chemical Formula 24]

[0200]

[0201] (In formula (1d), R1 represents a methyl group or an ethyl group.)

[0202] A nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluryl derivative represented by the following formula (1E).

[0203] [Chemical Formula 25]

[0204]

[0205] (In formula (1E), the 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.)

[0206] As a glycoluryl derivative represented by the above formula (1E), for example, compounds represented by the following formulas (1E-1) to (1E-6) may be cited.

[0207] [Chemical Formula 26]

[0208]

[0209] A nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule is obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) that bond to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0210] [Chemical Formula 27]

[0211]

[0212] (In formulas (2d) and (3d), R1 represents a methyl or ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.)

[0213] The glycoluryl derivative represented by the above formula (1E) is obtained by reacting the glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0214] A nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) in one molecule is, for example, a glycoluryl derivative represented by the following formula (2E).

[0215] [Chemical Formula 28]

[0216]

[0217] (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.)

[0218] As a glycoluryl derivative represented by the above formula (2E), examples include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, as a compound represented by the above formula (3d), examples include compounds represented by the following formulas (3d-1) and (3d-2).

[0219] [Chemical Formula 29]

[0220]

[0221] [Chemical Formula 30]

[0222]

[0223] Regarding the contents of nitrogen-containing compounds having 2 to 6 substituents represented by the following formula (1d) that bond to the above nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0224] In addition, the crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2), as described in International Publication No. 2014 / 208542.

[0225] [Chemical Formula 31]

[0226]

[0227] (In the food, Q 1 represents a single bond or an organic group of m1, and R 1 and R4 Each represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 represents a hydrogen atom or a methyl group, respectively, and R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms.

[0228] n1 represents an integer 1≤n1≤3, n2 represents an integer 2≤n2≤5, n3 represents an integer 0≤n3≤3, n4 represents an integer 0≤n4≤3, and 3≤(n1+n2+n3+n4)≤6.

[0229] n5 represents an integer 1≤n5≤3, n6 represents an integer 1≤n6≤4, n7 represents an integer 0≤n7≤3, n8 represents an integer 0≤n8≤3, and 2≤(n5+n6+n7+n8)≤5.

[0230] m1 represents an integer from 2 to 10.

[0231] The crosslinkable compound represented by the above formula (G-1) or formula (G-2) may be obtained by the reaction of a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0232] [Chemical Formula 32]

[0233]

[0234] (In the food, Q 2 represents a single bond or an organic group of m2. R 8 , R 9 , R 11 and R 12 represents a hydrogen atom or a methyl group, respectively, and 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.

[0235] n9 represents an integer such that 1≤n9≤3, n10 represents an integer such that 2≤n10≤5, n11 represents an integer such that 0≤n11≤3, n12 represents an integer such that 0≤n12≤3, and 3≤(n9+n10+n11+n12)≤6.

[0236] n13 represents an integer such that 1≤n13≤3, n14 represents an integer such that 1≤n14≤4, n15 represents an integer such that 0≤n15≤3, n16 represents an integer such that 0≤n16≤3, and 2≤(n13+n14+n15+n16)≤5.

[0237] m2 represents an integer from 2 to 10.

[0238] Compounds represented by the above formulas (G-1) and (G-2) can be exemplified below.

[0239] [Chemical Formula 33]

[0240]

[0241] [Chemical Formula 34]

[0242]

[0243] [Chemical Formula 35]

[0244]

[0245] [Chemical Formula 36]

[0246]

[0247] [Chemical Formula 37]

[0248]

[0249] Compounds represented by formulas (G-3) and (G-4) can be exemplified below.

[0250] [Chemical Formula 38]

[0251]

[0252] [Chemical Formula 39]

[0253]

[0254] In the formula, Me represents a methyl group.

[0255] The full disclosure of International Publication No. 2014 / 208542 is made by reference to this institution.

[0256] When the above crosslinking agent is used, the content ratio of the said crosslinking agent is, for example, 1 mass% to 50 mass% with respect to the reaction product, and preferably 5 mass% to 30 mass%.

[0257] Other ingredients

[0258] In the resist underlayer forming composition of the present invention, a surfactant may be additionally added to further improve the applicability against surface stains and prevent the occurrence of pinholes or streaks. As surfactants, for example, nonionic surfactants such as polyoxyethylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkylallyl ethers including polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters including sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters including polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, F-Top EF301, Examples include fluorine-based surfactants such as EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), MegaPac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants incorporated is typically 2.0 mass% or less, preferably 1.0 mass% or less, with respect to the total solid content of the resist underlayer forming composition of the present invention. These surfactants may be added individually or in combination of two or more types.

[0259] The solid content included in the resist underlayer forming composition of the present invention, that is, the component excluding the solvent, is, for example, 0.01 mass% to 10 mass%.

[0260] <Resist Sublayer>

[0261] The resist lower layer film according to the present invention can be manufactured by applying the aforementioned resist lower layer forming composition onto a semiconductor substrate and firing it.

[0262] Examples of semiconductor substrates to which the resist underlayer forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0263] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0264] The resist underlayer forming composition of the present invention is applied onto such a semiconductor substrate by a suitable application method, such as a spinner or a coater. Afterward, a resist underlayer is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0265] The film thickness of the formed resist underlayer is, for example, 0.001μm (1nm) to 10μm, 0.002μm (2nm) to 1μm, 0.005μm (5nm) to 0.5μm (500nm), 0.001μm (1nm) to 0.05μm (50nm), 0.002μm (2nm) to 0.05μm (50nm), 0.003μm (3nm) to 0.05μm (50nm), 0.004μm (4nm) to 0.05μm (50nm), 0.005μm (5nm) to 0.05μm (50nm), 0.003μm (3nm) to 0.03μm (30nm), 0.003μm (3nm) to 0.02μm (20nm). The ranges are 0.005μm (5nm) to 0.02μm (20nm), 0.003μm (3nm) to 0.01μm (10nm), 0.005μm (5nm) to 0.01μm (10nm), 0.003μm (3nm) to 0.006μm (6nm), and 0.005μm (5nm). If the baking temperature is lower than the above ranges, crosslinking becomes insufficient. On the other hand, if the baking temperature is higher than the above ranges, the resist underlayer may decompose due to heat.

[0266] Method for manufacturing a patterned substrate, method for manufacturing a semiconductor device

[0267] The method for manufacturing a patterned substrate involves the following process. Typically, it is manufactured by forming a photoresist layer on a resist underlayer. The photoresist formed by applying and firing on the resist underlayer by a known method is not particularly limited as long as it is sensitized to the light used for exposure. Either a negative-type photoresist or a positive-type photoresist may be used. Examples include positive type photoresists composed of novolak resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemical amplification type photoresists composed of a binder having a group that decomposes by acid to increase the alkali dissolution rate and a photogenerator, chemical amplification type photoresists composed of a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photogenerator, and chemical amplification type photoresists composed of a binder having a group that decomposes by acid to increase the alkali dissolution rate of the photoresist, a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, and a photogenerator, and resists containing metal elements. Examples include JSR Corporation's product name V146G, Seaplay's product name APEX-E, Sumitomo Chemical Corporation's product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430. In addition, fluorine-containing polymer-based photoresists such as those described in Proc.SPIE, Vol. 3999, 330-334 (2000), Proc.SPIE, Vol. 3999, 357-364 (2000), or Proc.SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0268] Additionally, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Patent Publication 2018-180525, WO2018 / 190088, Japanese Patent Publication 2018-070596, Japanese Patent Publication 2018-028090, Japanese Patent Publication 2016-153409, Japanese Patent Publication 2016-130240, Japanese Patent Publication 2016-108325, Japanese Patent Publication 2016-047920, Japanese Patent Publication 2016-035570, Japanese Patent Publication 2016-035567, Japanese Patent Publication 2016-035565, Japanese Patent Publication 2019-101417, Japanese Patent Publication 2019-117373, Japanese Patent Publication 2019-052294, Japanese Patent Publication 2019-008280, Japanese Patent Publication 2019-008279, Japanese Patent Publication 2019-003176, Japanese Patent Publication 2019-003175, Japanese Patent Publication 2018-197853, Japanese Patent Publication 2019-191298, Japanese Patent Publication 2019-061217, Japanese Patent Publication 2018-045152, Japanese Patent Publication 2018-022039, Japanese Patent Publication 2016-090441, Japanese Patent Publication 2015-10878, Japanese Patent Publication 2012-168279, Japanese Patent Publication 2012-022261, Japanese Patent Publication 2012-022258, Japanese Patent Publication 2011-043749, Japanese Patent Publication 2010-181857, Japanese Patent Publication 2010-128369, WO2018 / 031896, Japanese Patent Publication 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Publication 2018-41099,So-called resist compositions and metal-containing resist compositions, such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions, as described in WO2016 / 065120, WO2015 / 026482, Japanese Patent Publication 2016-29498, Japanese Patent Publication 2011-253185, etc., may be used, but are not limited thereto.

[0269] Examples of resist compositions include the following compositions.

[0270] A resin A having repeating unit having a polar group protected by an acid-degradable group that is detached by the action of acid, and a compound represented by the general formula (21), comprising a desensitizing light-sensitive or radiation-sensitive resin composition.

[0271] [Chemical Formula 40]

[0272]

[0273] In the general formula (21), m represents an integer from 1 to 6.

[0274] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0275] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0276] L2 represents an alkylene group or a single bond that may have a substituent.

[0277] W1 represents a cyclic organic group that may have a substituent.

[0278] M + represents a cation.

[0279] A metal-containing film forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to periods 3 through 7 of groups 3 through 15 of the periodic table.

[0280] A radiation-reducing 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 including an acid-dissociating group, and an acid-generating agent.

[0281] [Chemical Formula 41]

[0282]

[0283] (In Equation (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. R 1 It is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R 1 is the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 Silver is a monovalent group having 1 to 20 carbon atoms containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0284] A resist composition containing a resin (A1) comprising a structural unit having a cyclic carbonate ester structure, a structural unit represented by the following formula, and a structural unit having an acid instability group, and an acid-generating agent.

[0285] [Chemical Formula 42]

[0286]

[0287] [During the meal,

[0288] R 2 represents a carbon-1 to carbon-6 alkyl group that may have a halogen atom, a hydrogen atom, or a halogen atom, and X 1 Silver, single bond, -CO-O-* or -CO-NR 4 -* represents, * represents the number of bonds with -Ar, and R 4represents 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 that may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0289] Examples of resist films include the following.

[0290] A resist film comprising a base resin including a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain by exposure.

[0291] [Chemical Formula 43]

[0292]

[0293] (among Equations (a1) and (a2), R A is, independently, a hydrogen atom or a methyl group. R 1 and R 2 R is, each independently, a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each is independently a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a linker having 1 to 12 carbon atoms comprising at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond, a lactone ring, a phenylene group, and a naphthylene group. X 2 is a single bond, ester bond, or amide bond.)

[0294] Examples of resist materials include the following.

[0295] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0296] [Chemical Formula 44]

[0297]

[0298] (among Equations (b1) and (b2), R Ais a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 is a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and also, X 2 At least one hydrogen atom included in is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and a portion of the methylene group constituting this alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They can also combine to form a carbonyl group. R 1 ~R 5 Each is independently a straight-chain, branched, or cyclic C1-12 alkyl group, a straight-chain, branched, or cyclic C2-12 alkenyl group, C2-12 alkynyl group, C6-20 aryl group, C7-12 aralkyl group, or C7-12 aryloxyalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sulfonate group, a sulfonium salt-containing group, or some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. Additionally, R 1 and R 2 They can combine and form a ring together with the sulfur atoms they combine with.

[0299] A resist material comprising a base resin comprising a polymer comprising repeating units represented by the following formula (a).

[0300] [Chemical Formula 45]

[0301]

[0302] (in Equation (a), R A is a hydrogen atom or a methyl group. R 1 It is silver, a hydrogen atom, or an acid instable. R 2 is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond, a phenylene group, an ester group, or a lactone ring. X 2 is -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. n is an integer from 0 to 3.)

[0303] A resist composition that generates acid upon exposure and changes solubility in a developer solution through the action of the acid,

[0304] It contains a substrate component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, and

[0305] A resist composition characterized in that the above-mentioned fluorine additive component (F) contains a fluorine resin component (F1) having a constituent unit (f1) containing a base-dissociating group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).

[0306] [Chemical Formula 46]

[0307]

[0308] [In Equation (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 the number of bonds.]

[0309] The above-mentioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0310] [Chemical Formula 47]

[0311]

[0312] [In formulas (f1-1) and (f1-2), R is, respectively, independently a hydrogen atom, a C1-5 alkyl group, or a C1-5 alkyl halide group. X is a divalent linker that does not have an acid-dissociable site. A aryl It is a divalent aromatic cyclic group that may have substituents. X 01 It is a single bond or a divalent linker. R 2 is an organic group having a fluorine atom, each independently.

[0313] Examples of coatings, coating solutions, and coating compositions include the following.

[0314] A coating comprising a metal oxo-hydroxo network having organic ligands formed by metal-carbon bonds and / or metal-carboxylate bonds.

[0315] Inorganic iodine / hydroxo base composition.

[0316] As a coating solution, an organic solvent; as a first organometallic composition, Formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (here, 0 <z≤2 및 0<(z+x)≤4이다), 식R’ n SnX 4-n A first organometallic composition represented by (where n=1 or 2), or a mixture thereof, wherein R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolytic bond to Sn or a combination thereof; and as a hydrolytic metal compound, formula MX' vA coating solution comprising a hydrolyzable metal compound represented by (wherein M is a metal selected from groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable MX bond or a combination thereof).

[0317] Organic solvent and formula RSnO (3 / 2-x / 2) (OH) x (While eating, 0 <x<3)로 표시되는 제1 유기금속 화합물을 포함하는 코팅 용액으로서, 상기 용액 중에 약 0.0025M~약 1.5M의 주석이 포함되고, R이 3~31개의 탄소원자를 갖는 알킬기 또는 시클로알킬기이고, 상기 알킬기 또는 시클로알킬기가 제2급 또는 제3급 탄소원자에 있어서 주석에 결합된, 코팅 용액.

[0318] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-reducing ligand comprising a peroxide group.

[0319] Exposure is performed through a mask (reticle) to form a predetermined pattern, and, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. The resist underlayer forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and preferably applied for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time from 10 seconds to 300 seconds. As an alkaline developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., an aqueous solution of an alkali such as a primary amine such as ethylamine, n-propylamine, etc., a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, etc., an alcohol amine such as dimethylethanolamine, triethanolamine, etc., a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., or a cyclic amine such as pyrrole, piperidine, etc., may be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol, or a nonionic surfactant, may be added to the above aqueous solution of alkali. Among these, a preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Furthermore, a surfactant, etc., may be added to these developers. Instead of an alkaline developer, a method may be used to develop using an organic solvent such as butyl acetate, and to develop the areas where the alkaline dissolution rate of the photoresist is not enhanced. Through the above process, a substrate patterned with the resist can be manufactured.

[0320] Next, the resist lower layer is dry-etched using the formed resist pattern as a mask. At that time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the substrate can be manufactured by undergoing a process of processing the substrate using a known method (such as a dry etching method).

[0321] Examples

[0322] Next, the contents of the present invention will be specifically explained with reference to examples, but the present invention is not limited to these.

[0323] The weight-average molecular weight of the polymers shown in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, Synthesis Example 4, and Comparative Synthesis Example 1 of this specification is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosho Inc. was used for the measurement, and the measurement conditions, etc. are as follows.

[0324] GPC Column: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.)

[0325] Column temperature: 40℃

[0326] Solvent: Tetrahydrofuran (THF)

[0327] Flow rate: 1.0 ml / min

[0328] Standard sample: Polystyrene (manufactured by Toso Co., Ltd.)

[0329] <Synthesized Example 1>

[0330] 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 3.01 g of 3,3'-dithiodipropionic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd., trade name: DTDPA), 0.59 g of morpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 0.20 g of tetrabutylphosphonium bromide (manufactured by ACROSS) were added to 12.56 g of propylene glycol monomethyl ether and dissolved. After nitrogen purging the reaction vessel, the reaction was carried out at 80°C for 24 hours to obtain a polymer solution. The polymer solution did not exhibit turbidity or other issues even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 5,000 in standard polystyrene equivalent. The structure present in the polymer obtained in this synthesis example is shown in the following formula.

[0331] [Chemical Formula 48]

[0332]

[0333] <Synthesized Example 2>

[0334] 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 3.18 g of 3,3'-dithiodipropionic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd., trade name: DTDPA), 0.47 g of 4-dimethylaminobenzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 0.20 g of tetrabutylphosphonium bromide (manufactured by ACROSS) were added to 13.29 g of propylene glycol monomethyl ether and dissolved. After nitrogen purging the reaction vessel, the reaction was carried out at 80°C for 24 hours to obtain a polymer solution. The polymer solution did not produce turbidity or the like even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 6,000 in standard polystyrene equivalent. The structure present in the polymer obtained in this synthesis example is shown in the following formula.

[0335] [Chemical Formula 49]

[0336]

[0337] <Synthesized Example 3>

[0338] 20.00 g of monoallyl diglycidyl isocyanuric acid (Shikoku Kasei Kogyo Co., Ltd.), 11.16 g of diethyl barbital (Hachidai Pharma Co., Ltd.), 1.86 g of morpholine (Tokyo Kasei Kogyo Co., Ltd.), and 0.83 g of tetrabutylphosphonium bromide (ACROSS) were added to 50.78 g of propylene glycol monomethyl ether and dissolved. After nitrogen purging the reaction vessel, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. The polymer solution did not exhibit turbidity or other abnormalities even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 5,000 in standard polystyrene equivalent. The structure present in the polymer obtained in this synthesis example is shown in the following formula.

[0339] [Chemical Formula 50]

[0340]

[0341] <Synthesized Example 4>

[0342] 5.00 g of monoallyl diglycidyl isocyanuric acid (Shikoku Kasei Kogyo Co., Ltd.), 2.80 g of diethyl barbital (Hachidai Pharma Co., Ltd.), 0.89 g of 4-dimethylaminobenzoic acid (Tokyo Kasei Kogyo Co., Ltd.), and 0.20 g of tetrabutylphosphonium bromide (ACROSS) were added to 13.34 g of propylene glycol monomethyl ether and dissolved. After nitrogen purging the reaction vessel, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. The polymer solution did not exhibit turbidity or other abnormalities even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 6,000 in standard polystyrene equivalent. The structure present in the polymer obtained in this synthesis example is shown in the following formula.

[0343] [Chemical Formula 51]

[0344]

[0345] <Comparative Synthesis Example 1>

[0346] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 1.91 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 0.57 g of adamantanecarboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by ACROSS) were added to 6.87 g of propylene glycol monomethyl ether and dissolved. After nitrogen purging the reaction vessel, the reaction was carried out at 80°C for 24 hours to obtain a polymer solution. The polymer solution did not exhibit turbidity or other issues even when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 5,000 in standard polystyrene equivalent. The structure present in the polymer obtained in this synthesis example is shown in the following formula.

[0347] [Chemical Formula 52]

[0348]

[0349] <Example 1>

[0350] 0.27 g of p-toluenesulfonic acid (100 mol% relative to the polymer ends) was added to 10.00 g of the polymer solution (solid content: 20.0 wt%) obtained in Synthesis Example 1 above, and the mixture was stirred at room temperature for 24 hours. By stirring for 24 hours, p-toluenesulfonic acid was coordinated to the morpholine in the polymer. Subsequently, the mixture was reprecipitated in 2-propanol to remove any uncoordinated p-toluenesulfonic acid. The removal was confirmed by GPC. The obtained polymer solid was dissolved in propylene glycol monomethyl ether to form a solution. The structure of the polymer present in the polymer solution obtained in this example is shown in the following formula.

[0351] [Chemical Formula 53]

[0352]

[0353] <Example 2>

[0354] To 0.43 g (solid content: 16.4 wt%) of the polymer solution obtained in Example 1 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 44.5 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0355] <Example 3>

[0356] 0.27 g of p-toluenesulfonic acid (100 mol% relative to the polymer ends) was added to 10.00 g of the polymer solution (solid content: 20.0 wt%) obtained in Synthesis Example 2 above, and the mixture was stirred at room temperature for 24 hours. By stirring for 24 hours, p-toluenesulfonic acid was coordinated to the morpholine in the polymer. Subsequently, the mixture was reprecipitated in 2-propanol to remove any uncoordinated p-toluenesulfonic acid. The removal was confirmed by GPC. The obtained polymer solid was dissolved in propylene glycol monomethyl ether to form a solution. The polymer structure present in the polymer solution obtained in this example is represented by the following formula.

[0357] [Chemical Formula 54]

[0358]

[0359] <Example 4>

[0360] To 0.43 g (solid content: 16.4 wt%) of the polymer solution obtained in Example 3 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 44.5 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0361] <Example 5>

[0362] To 0.48 g (solid content: 20.0 wt%) of the polymer solution obtained in Synthesis Example 3 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 0.02 g of p-toluenesulfonic acid (100 mol%) relative to the polymer end, 44.4 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0363] <Example 6>

[0364] To 0.48 g (solid content: 20.0 wt%) of the polymer solution obtained in Synthesis Example 4 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 0.02 g of p-toluenesulfonic acid (100 mol%) relative to the polymer end, 44.4 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0365] <Comparative Example 1>

[0366] 0.27 g of p-toluenesulfonic acid (100 mol% relative to the polymer end) was added to 10.00 g of the polymer solution (solid content: 20.0 wt%) obtained in Comparative Synthesis Example 1 above, and the mixture was stirred at room temperature for 24 hours. Afterward, the mixture was reprecipitated in 2-propanol to remove the uncoordinated p-toluenesulfonic acid. The removal was confirmed by GPC. The obtained polymer solid was dissolved in propylene glycol monomethyl ether to form a solution.

[0367] <Comparative Example 2>

[0368] To 0.43 g (solid content: 16.4 wt%) of the polymer solution obtained in Comparative Example 1 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 44.5 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0369] <Comparative Example 3>

[0370] To 0.47 g (solid content: 20.0 wt%) of the polymer solution obtained in Comparative Synthesis Example 1 above, 0.02 g of tetramethoxymethylglycoluryl (manufactured by Japan Cytec Industries Co., Ltd.), 0.003 g of pyridinium phenolsulfonic acid, 44.6 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, the mixture was filtered using a polyethylene microfilter with a pore diameter of 0.05 μm to form a composition for forming a resist underlayer for lithography.

[0371] [Dissolution Test into Photoresist Solvent]

[0372] The resist sublayer forming compositions of Examples 2, 4, 5, 6, Comparative Example 2, and Comparative Example 3 were each applied onto a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist sublayer (film thickness 5 nm). These resist sublayers were immersed in ethyl sulfate and propylene glycol monomethyl ether, which are solvents used for photoresist, and were classified as good if the film thickness change was less than 1 Å and poor if it was 1 Å or more, and the results are shown in Table 1.

[0373] [Table 1]

[0374]

[0375] From these results, it was suggested that in Examples 2 and 4, p-toluenesulfonic acid was coordinated and supported on the polymer to form a salt. On the other hand, Comparative Example 2 suggested that p-toluenesulfonic acid was not coordinated and supported on the polymer. In addition, in Examples 4 and 5, sufficient solvent resistance was exhibited even when p-toluenesulfonic acid was added during formulation.

[0376] [Formation of a negative type resist pattern by an electron beam lithography device]

[0377] The resist sublayer forming compositions of Examples 2, 4, 5, 6, and Comparative Example 3 were each applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist sublayer with a thickness of 5 nm. A positive-type EUV resist solution (containing methacrylate polymer) was spin-coated onto the resist sublayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed to light under predetermined conditions using an electron beam lithography device (ELS-G130). After exposure, baking (PEB) was performed at 100°C for 60 seconds, cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with a 26 nm filler pattern and a 52 nm pitch. A scanning electron microscope (CG4100, manufactured by Hitachi High Technologies Co., Ltd.) was used to measure the resist pattern. The photoresist pattern obtained in this way was observed from the top of the pattern and evaluated. In the formation of the resist pattern, if the filler pattern could be formed, it was indicated as "Good," and if the filler pattern collapsed or peeled, it was indicated as "Poor." In addition, the amount of exposure required to form a CD-size 26 nm filler pattern was compared.

[0378] [Table 2]

[0379]

[0380] The results suggest that lithography performance can be improved by supporting a thermal acid generator, which promotes conventional crosslinking reactions, on a polymer.

[0381] Industrial applicability

[0382] The resist underlayer forming composition according to the present invention can provide a composition for forming a resist underlayer capable of forming a desired resist pattern, and a method for manufacturing a resist pattern-attached substrate and a semiconductor device using the resist underlayer forming composition.

Claims

Claim 1 A polymer comprising an acid compound supported on a terminal and a solvent, wherein the terminal is of the following formula (I): [Among Equation (I), A 1 Equation (III): A resist underlayer forming composition represented by [wherein in Formula (III), A is a straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group that may be substituted, an aryl group that may be substituted by a group other than a carboxyl group, or a heteroaryl group that may be substituted], B represents a basic structure, and * is a binding site with a polymer residue]. Claim 2 delete Claim 3 delete Claim 4 A resist underlayer forming composition according to claim 1, wherein B comprises a nitrogen atom. Claim 5 In paragraph 1, the above B is R 1 R 2 R 3 N and R 1 , and R 2 Each represents a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and R 1 and R 2 It may form a ring with or without heteroatoms, and R 3 represents an aromatic group that may be substituted, or a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may be substituted, and R 1 and R 2 When is not forming a ring, R 3 A resist underlayer forming composition, wherein the aromatic group may be substituted. Claim 6 In paragraph 1, the above B, [In the middle of the meal, R 1 , and R 2 Each represents a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group that may or may not be substituted, and R 3 represents an aromatic group that may be substituted.], or the following formula (II) [In formula (II), R is a hydrogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a combination thereof, and R' is, and, R a and R b A resist underlayer forming composition, which is a base represented by [where each independently represents an arbitrarily substituted alkyl, X is O, S, or SO2, and n and m are each independently 2, 3, 4, 5, or 6]. Claim 7 In paragraph 6, the above R 3 This represents a phenyl, naphthyl, anthracenyl, or phenanthrenyl group that may be substituted, wherein R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group, and R' is, A resist underlayer forming composition, which is a base represented by Claim 8 delete Claim 9 In claim 1, the polymer is of the following formula (1): [In the formulas, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 is formula (2), formula (3), formula (4), or formula (0): (In the formula, R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, and a phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 6 carbon atoms; additionally, R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, And, the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms), and Q represents Formula (5) or Formula (6): [A resist having a repeating unit structure represented by the formula [wherein Q1 represents an alkylene group, a phenylene group, a naphthylene group, or anthrylene group having 1 to 10 carbon atoms, and the alkylene group, phenylene group, naphthylene group, and anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a combination thereof, and the alkylene group may be interrupted by a disulfide bond, n1 and n2 each represent a number of 0 or 1, and X2 represents formula (2), formula (3), or formula (0)] Sublayer forming composition. Claim 10 A resist underlayer forming composition comprising, in addition to a crosslinking agent, a component of claim 1. Claim 11 A resist underlayer forming composition comprising, in addition to an acid-generating agent, a component of claim 1. Claim 12 A resist underlayer characterized by being a sintered product of a coating film formed from a resist underlayer forming composition described in any one of claims 1, 4 to 7 and 9 to 11. Claim 13 A method for manufacturing a patterned substrate, comprising: a process of forming a resist lower layer film by applying a resist lower layer forming composition described in any one of claims 1, 4 to 7 and 9 to 11 onto a semiconductor substrate and baking; a process of forming a resist film by applying a resist onto the resist lower layer film and baking; a process of exposing the resist lower layer film and the semiconductor substrate coated with the resist to light; and a process of developing and patterning the resist film after exposure. Claim 14 A method for manufacturing a semiconductor device, characterized by comprising: a process of forming a resist sublayer film on a semiconductor substrate, the resist sublayer film being formed from a resist sublayer film forming composition described in any one of claims 1, 4 to 7, and 9 to 11; a process of forming a resist film on the resist sublayer film; a process of forming a resist pattern by irradiating the resist film with light or electron beams and subsequently developing; a process of forming a patterned resist sublayer film by etching the resist sublayer film through the formed resist pattern; and a process of processing the semiconductor substrate using the patterned resist sublayer film.

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