Resist underlayer film forming composition

Abstract

To provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a resist pattern using the resist underlayer film-forming composition, and a method for producing a semiconductor device.SOLUTION: There is provided a resist underlayer film-forming composition comprising a polymer and a solvent, the composition including, at a terminal of the polymer, a structure represented by formula (103): (in formula (103), Ar represents a C6-40 aromatic ring group which may be substituted, L1 represents a single bond, an ester bond, an ether bond, a C1-10 alkylene group, or a C2-10 alkenylene group, and n represents an integer of 1-3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to compositions used in lithography processes in semiconductor manufacturing, particularly in state-of-the-art lithography processes (ArF, EUV, EB, etc.). It also relates to a method for manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device. [Background technology]

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film to form fine irregularities on the substrate surface corresponding to the pattern. In recent years, semiconductor devices have become more highly integrated, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation due to influence from the semiconductor substrate has become a major problem. Therefore, in order to solve this problem, methods for providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated. Patent Document 1 discloses a resist underlayer film forming composition for EUV lithography having a condensation polymer. Patent Document 2 discloses a resist underlayer film forming composition containing a polymer having a specific unit structure in its main chain. Patent Document 3 discloses a semiconductor lithography film forming composition containing a nitrile compound. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Patent Application Publication No. 2013 / 018802 [Patent Document 2] Japanese Patent Publication No. 2015-145944 [Patent Document 3] International Patent Application Publication No. 2019 / 059202 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The required properties for the resist underlayer include, for example, that it does not intermix with the resist film formed on top (i.e., it is insoluble in the resist solvent) and that it has a faster dry etching rate compared to the resist film.

[0005] In lithography involving EUV exposure, the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is formed and used with a thinner film thickness than conventional methods. When forming such thin films, pinholes and aggregation are likely 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] On the other hand, in the development process for forming resist patterns, a major challenge is improving the adhesion of the resist pattern in negative development processes, which use a solvent capable of dissolving the resist film, usually an organic solvent, to remove the unexposed parts of the resist film and leave the exposed parts as the resist pattern, and in positive development processes, which remove the exposed parts of the resist film and leave the unexposed parts as the resist pattern.

[0007] Furthermore, there is a need to suppress the deterioration of LWR (Line Width Roughness, fluctuations in line width (roughness)) during resist pattern formation, to form a resist pattern with a good rectangular shape, and to improve resist sensitivity.

[0008] The present invention aims to provide a composition for forming a resist underlayer film that can form a desired resist pattern, and a method for forming a resist pattern using the resist underlayer film forming composition, which solves the above problems. [Means for solving the problem]

[0009] This invention encompasses the following: [1] The following formula (100): [ka] (In formula (100), Ar represents an aromatic ring group with 6 to 40 carbon atoms, which may be substituted. L 0 represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms. T 0 represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms. However, L 0 and T 0 Unlike, n R 0 The terms independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group. n represents an integer from 0 to 5. * A resist underlayer film forming composition comprising a polymer or compound having a structure represented by (), and a solvent. [2] A compound comprising a substructure represented by formula (100), and a solvent, In equation (100), Ar represents an aromatic ring with 6 to 40 carbon atoms, which may be substituted. L 0represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms, T 0 represents a single bond, n R's 0 each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group, n represents an integer of 1 to 3 The resist lower layer film forming composition according to [1]. [3] The compound is a reaction product of an epoxy group-containing compound and a compound represented by the following formula (101):

Chemical formula

Chemical formula

Chemical formula

[10] The following formula (200): [ka] (In formula (200), Ar represents an aromatic ring with 6 to 40 carbon atoms that may be substituted, L 2 represents an alkenylene group with 2 to 10 carbon atoms, which may be substituted, and n R 2 A resist underlayer film forming composition comprising a polymer or compound having a structure represented by ) at its terminus, and a solvent.

[11] The polymer is a reaction product of a compound (A) containing two or more epoxy groups and a compound (B) containing two or more groups that are reactive with the epoxy groups. The resist underlayer forming composition according to

[10] , wherein the compounds (A) and (B) comprise a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

[12] The aforementioned polymer is given by the following formula (P2): [ka] (In formula (P2), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, Q 1 and Q 2 Each of these independently represents a divalent organic group containing a heterocyclic structure or an aromatic ring structure with 6 to 40 carbon atoms, T 2 and T 3 Each of these independently represents a single bond, an ester bond, or an ether bond, L 2 and L 3Each of these independently represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms.) A resist underlayer forming composition according to

[10] or

[11] , comprising a unit structure represented by ).

[13] The following formula (300): [ka] (In formula (300), Ar represents an aryl group having 6 to 40 carbon atoms, which may be substituted, L 3 T represents a single bond, ester bond, or ether bond. 3 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted, and n R 3 represents an independent monovalent organic group, and n represents an integer from 0 to 5. * A resist underlayer film forming composition comprising a polymer having a structure represented by formula (300) at its terminus, where represents a binding site with a polymer residue and contains at least one cyano group, and a solvent.

[14] The aforementioned polymer is given by the following formula (P3): [ka] (In formula (P3), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, Q 1 represents a divalent organic group, T 2 and T 3 Each of these independently represents a single bond, an ester bond, or an ether bond, L 2 and L 3The resist underlayer forming composition described in

[13] is represented as follows: each independently represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; D represents an arylene group or heterocycle having 6 to 40 carbon atoms; U represents a group selected from the group consisting of a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms; and m represents an integer from 0 to 5.

[15] A resist underlayer film forming composition according to any one of [1] to

[14] , further comprising an acid generator.

[16] A resist underlayer film forming composition according to any one of [1] to

[15] , further comprising a crosslinking agent.

[17] A resist underlayer film characterized by being a fired product of a coated film made from any one of the resist underlayer film forming compositions described in [1] to

[16] .

[18] A step of forming a resist underlayer film by applying a resist underlayer film forming composition described in any one of items [1] to

[16] onto a semiconductor substrate and baking it, A step of forming a resist film by coating the resist on the resist underlayer film and baking it. A step of exposing the resist underlayer film and the semiconductor substrate coated with the resist, The process of developing and patterning the resist film after exposure. A method for manufacturing patterned substrates, including [the specified method].

[19] A step of forming a resist underlayer on a semiconductor substrate, comprising a resist underlayer forming composition according to any one of items [1] to

[16] , A step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following: [Effects of the Invention]

[0010] The resist underlayer film forming composition of the present invention has excellent coatability on semiconductor substrates to be processed and excellent adhesion between the resist and the resist underlayer film interface during resist pattern formation. This prevents peeling of the resist pattern, suppresses deterioration of LWR (Line Width Roughness) during resist pattern formation, enables minimization of the resist pattern size (minimum CD size), and allows for the formation of a good resist pattern with a rectangular shape. This effect is particularly pronounced when using EUV (wavelength 13.5 nm) or EB (electron beam). [Modes for carrying out the invention]

[0011] <Resist Underlayer Film Forming Composition> The resist underlayer film forming composition of the present invention is given by the following formula (100): [ka] (In formula (100), Ar represents an aromatic ring group with 6 to 40 carbon atoms, which may be substituted. L 0 represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms. T 0 represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms. However, L 0 and T 0Unlike, n R 0 The terms independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group. n represents an integer from 0 to 5. * The symbol represents the binding portion with the polymer or compound residue. The material includes polymers or compounds containing the structure represented by ( ), and solvents.

[0012] Examples of aromatic rings having 6 to 40 carbon atoms include aromatic rings derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, and dibenzo[a,j]anthracene. Among these, selection from benzene, naphthalene, and anthracene is preferred.

[0013] Examples of aryl groups having 6 to 40 carbon atoms include 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-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0014] Arylene groups having 6 to 40 carbon atoms include phenylene group, o-methylphenylene group, m-methylphenylene group, p-methylphenylene group, o-chlorphenylene group, m-chlorphenylene group, p-chlorphenylene group, o-fluorophenylene group, p-fluorophenylene group, o-methoxyphenylene group, p-methoxyphenylene group, p-nitrophenylene group, p-cyanophenylene group, α-naphthylene group, β-naphthylene group, o-biphenylylene group, m-biphenylylene group, p-biphenylylene group, 1-antrylene group, 2-antrylene group, 9-antrylene group, 1-phenanthrylene group, 2-phenanthrylene group, 3-phenanthrylene group, 4-phenanthrylene group, and 9-phenanthrylene group.

[0015] The alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylcyclopropylene, 2-methylcyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, and 1-ethyl-n-propylene. Polyethylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group , 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene n group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples include 3-trimethylcyclopropylene group, 1-ethyl-2-methylcyclopropylene group, 2-ethyl-1-methylcyclopropylene group, 2-ethyl-2-methylcyclopropylene group, 2-ethyl-3-methylcyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group, or n-decanylene group.

[0016] The aforementioned alkenylene group having 2 to 10 carbon atoms includes groups among the alkylene groups having 2 to 10 carbon atoms that have at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms. Among the alkenylene groups having 2 to 10 carbon atoms, vinylene groups are preferred.

[0017] Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0018] The phrase "may be substituted" means that some or all of the hydrogen atoms present in the aromatic ring or aryl group having 6 to 40 carbon atoms, the alkylene group having 1 to 10 carbon atoms, or the alkenylene group having 2 to 10 carbon atoms may be substituted with, for example, a hydroxyl group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0019] The alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. Group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 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, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, and decyl group. Examples of alkenyl groups having 2 to 10 carbon atoms include groups among the alkyl groups having 2 to 10 carbon atoms that have at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms.

[0020] The alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, and 4-methyl-n - Examples include pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 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, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, and n-decanyloxy group.

[0021] <Resist underlayer film forming composition A (containing compound)> The resist underlayer film forming composition of the present invention A compound comprising a substructure represented by formula (100), and a solvent, In equation (100), Ar represents an aromatic ring with 6 to 40 carbon atoms, which may be substituted. L 0 This represents a single bond, an ester bond, an ether bond, an alkylene group with 1 to 10 carbon atoms, or an alkenylene group with 2 to 10 carbon atoms. T 0 This represents a single bond, n R 0 The terms independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group. n represents an integer between 1 and 3. It includes resist underlayer film forming composition A.

[0022] The aforementioned compound is an epoxy group-containing compound and the following formula (101): [ka] (In formula (101), R 1 The group that reacts with the epoxy group is Ar, L 1 And n are Ar and L in the above equation (100). 0 , and are synonymous with n, preferably Ar represents an aromatic ring with 6 to 40 carbon atoms, which may be substituted, and L 1 The compound may be a reaction product with a compound represented by ).

[0023] The epoxy group having a reactive group (R 1 Examples of epoxy groups include hydroxyl groups, acyl groups, acetyl groups, formyl groups, benzoyl groups, carboxyl groups, carbonyl groups, amino groups, imino groups, cyano groups, azo groups, azi groups, thiol groups, sulfo groups, and allyl groups. Among these, hydroxyl groups or carboxyl groups are preferred from the viewpoint of reactivity with epoxy groups.

[0024] Examples of the epoxy group-containing compounds include the following: [ka] [ka] [ka]

[0025] The following are examples of compounds represented by the above formula (101): [ka] [ka]

[0026] The lower limit of the weight-average molecular weight of the compound, as measured by gel permeation chromatography, for example, as described in the examples, is, for example, 200 or 300, and the upper limit of the weight-average molecular weight of the compound is, for example, 1,999, 1,500, or 1,200.

[0027] <Resist Underlayer Film Forming Composition A (Polymer-containing)> The resist underlayer forming composition of the present invention comprises a polymer and a solvent, and may include the structure represented by the above formula (100) at the polymer end.

[0028] (polymer) The polymer (polymer, resin) contained in the resist underlayer film forming composition of the present invention is not limited as long as it achieves the effects of the present invention, but for example, it may be a polymer having the following structure as described in WO2009 / 008446. Formula (1): [ka] (In the formula, R1 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom; n represents an integer from 0 to 4; R2 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom; X represents an ether bond or an ester bond; A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; and Q represents a divalent organic group between two carbon atoms.) A polymer having a repeating unit structure represented by .

[0029] Furthermore, the following formula (1) is described in WO2011 / 074494: [ka] [In the formula, X represents an ester bond or an ether bond. A1, A2, A3, A4, A5, and A6 represent a hydrogen atom, a methyl group, or an ethyl group, respectively, and Q is formula (2) or formula (3): [ka] (wherein Q1 represents an alkylene group, phenylene group, naphthylene group, or anthrylene group having 1 to 10 carbon atoms, and the phenylene group, naphthylene group, and anthrylene group may each be substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms, n1 and n2 each represent the number 0 or 1, and X1 is formula (4), (5), or formula (6): [ka] The polymer may have a repeating unit structure represented by the formula (wherein R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the benzyl group and phenyl group may be substituted with a group selected from the group consisting of alkyl groups 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; R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms; R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the benzyl group and phenyl group may be substituted with a group selected from the group consisting of alkyl groups 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).

[0030] Furthermore, the polymer may have the following structure as described in WO2013 / 018802.

[0031] Formula (1a): [ka] [In the formulas, A1, A2, A3, A4, A5, and A6 represent a hydrogen atom, a methyl group, or an ethyl group, respectively, and X1 is formula (2), formula (3), formula (4), or formula (0): [ka] (In formulas (2), (3), (4), and (0), 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, the alkenyl group having 3 to 6 carbon atoms, the benzyl group, and the phenyl group are selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, and alkylthio groups having 1 to 6 carbon atoms) (The group may be substituted with a group, and 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 alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups and alkylthio groups having 1 to 6 carbon atoms), and Q represents formula (5) or formula (6): [ka] A polymer having a repeating unit structure represented by the formula (wherein Q1 represents an alkylene group, phenylene group, 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 group consisting of a combination thereof, and n1 and n2 each represent the number 0 or 1, and X2 represents formula (2), formula (3), or formula (0)).

[0032] Furthermore, the polymer of the present invention may be a resin described in WO2020 / 026834, having a repeating structural unit in the main chain containing at least one -C(=O)-O- group and a repeating structural unit in the side chain containing at least one hydroxyl group, or having a repeating structural unit in the main chain containing at least one -C(=O)-O- group and a repeating structural unit in the side chain containing at least one hydroxyl group.

[0033] Furthermore, the resin may be a copolymer having repeating structural units represented by the following formula (1-1) and repeating structural units represented by the following formula (1-2).

[0034] [ka] (In formulas (1-1) and (1-2), R 1 and R 2 Each of the following independently represents a divalent organic group containing a linear, branched, or cyclic functional group having 2 to 20 carbon atoms, and the organic group may have at least one sulfur atom, nitrogen atom, or oxygen atom; i and j independently represent 0 or 1; and the two Qs each represent a single bond, an -O- group, or an -C(=O)-O- group, provided that if both i and j are 0, at least one of the two Qs represents an -C(=O)-O- group. For example, the aforementioned resin is given by the following formula (A) [ka] (In formula (A), R 1 i and j have the same meaning as above.) At least one compound represented by the following formula (B) [ka] (In formula (B), R 2 A copolymer with at least one diexopy compound represented by ( ) can be used.

[0035] In other words, by dissolving at least one compound represented by formula (A) and at least one diepoxy compound represented by formula (B) in an organic solvent in an appropriate molar ratio, and polymerizing them in the presence of a catalyst if necessary, a copolymer having repeating structural units represented by formula (1-1) and repeating structural units represented by formula (1-2) can be obtained.

[0036] The compound represented by formula (A) is not particularly limited, but examples include the compound represented by the following formula. [ka] [ka]

[0037] The diexopie compound represented by formula (B) is not particularly limited, but examples of diexopie compounds include the following. [ka] [ka]

[0038] Copolymers having repeating structural units represented by formula (1-1) and formula (1-2) below include, for example, copolymers having repeating structural units represented by formulas (1a) to (1n) below. [ka] [ka]

[0039] The full disclosures of WO2009 / 008446, WO2011 / 074494, WO2013 / 018802, and WO2020 / 026834 are incorporated herein by reference.

[0040] The polymer is a compound containing two or more epoxy groups, and the following formula (102): [ka] (In formula (102), R 1 D represents a group that is reactive with epoxy groups, D represents an arylene group or heterocycle with 6 to 40 carbon atoms, and L 1 and n is L in the above equation (100). 0 This is synonymous with n, and preferably L 1 represents an alkenylene group with 2 to 10 carbon atoms, which may be substituted, and n R 1 The polymer may be obtained by reaction with a compound represented by ).

[0041] Compounds containing two or more epoxy groups are as described above.

[0042] Examples of the aforementioned heterocycles include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineon, triazinedione, and triazinetrione. Among these, triazineon, triazinedione, and triazinetrione are preferred.

[0043] The polymer may contain the structure represented by the above formula (100) at the polymer terminal.

[0044] The polymer is a polymer represented by the following formula (P):

Chemical formula

[0045] The epoxy group-containing compound, the compound containing two or more epoxy groups or Q 1 may contain a heterocyclic structure. Specific examples of the heterocyclic structure are as described above.

[0046] At least one of the above L 1 to L 3 may be an alkenylene group having 2 to 10 carbon atoms.

[0047] Among the alkenylene groups having 2 to 10 carbon atoms, a vinylene group is preferred.

[0048] The lower limit of the weight average molecular weight of the polymer, measured by gel permeation chromatography as described in, for example, the examples, is, for example, 1,000 or 2,000, and the upper limit of the weight average molecular weight of the polymer is, for example, 30,000, 20,000, or 10,000.

[0049] <Resist underlayer film forming composition B> The resist underlayer film forming composition of the present invention is represented by the following formula (200): [Chemical formula] (In formula (200), Ar represents an optionally substituted aromatic ring having 6 to 40 carbon atoms, and L 2 represents an optionally substituted alkenylene group having 2 to 10 carbon atoms. n R 2 s independently represent a group selected from the group consisting of a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms. n represents an integer of 0 to 5, and * represents a bonding moiety to a polymer or a compound residue.) A resist underlayer film forming composition B comprising a polymer or a compound containing a structure represented by the formula at a terminal, and a solvent.

[0050] The R 2 is preferably within 3 types selected from the above groups. The aromatic ring having 6 to 40 carbon atoms, the alkylene group having 1 to 10 carbon atoms, the alkenylene group having 2 to 10 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and the alkoxy group having 1 to 10 carbon atoms are as described above.

[0051] The structure of the formula (200) is preferably a structure derived from cinnamic acid.

[0052] The polymer may be a reaction product of a compound (A) containing two or more epoxy groups and a compound (B) containing two or more groups reactive with the epoxy group.

[0053] Specific examples of compound (A) containing two or more epoxy groups, and groups that are reactive with the epoxy groups, are as described above.

[0054] Specific examples of compound (B) containing two or more groups that are reactive with the epoxy group include the compounds listed below.

[0055] [ka] [ka]

[0056] The compounds (A) and (B) may include a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

[0057] The aforementioned complex ring structure is as described above.

[0058] Furthermore, the above heterocyclic structure may be derived from a barbituric acid.

[0059] The aromatic ring structure with 6 to 40 carbon atoms is as described above.

[0060] The aforementioned polymer is given by the following formula (P): [ka] (In formula (P), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, Q 1 and Q 2 Each of these independently represents a divalent organic group containing a heterocyclic structure or an aromatic ring structure with 6 to 40 carbon atoms, T 2 and T 3Each of these independently represents a single bond, an ester bond, or an ether bond, L 2 and L 3 Each of these independently represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted. The unit structure represented by ( ) may be included. The terms are as described above.

[0061] <Compound> The compound of this application is not limited as long as it is a compound that exhibits the effects of this application, but it contains the structure of formula (200) at the end of the compound. Specific examples of compound precursors for inducing the aforementioned compound residues include those exemplified by compound (A) containing two or more epoxy groups. The compound residue may include a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms. The aforementioned heterocyclic structure may be a triazinetrione.

[0062] <Resist Underlayer Film Forming Composition C> The resist underlayer film forming composition of the present invention is of the following formula (300): [ka] (In formula (300), Ar represents an aryl group having 6 to 40 carbon atoms, which may be substituted, L 3 T represents a single bond, ester bond, or ether bond. 3 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted, and n R 3 represents an independent monovalent organic group, and n represents an integer from 0 to 5. * The resist underlayer film forming composition C comprises a polymer having a structure represented by (300) at its terminus, which represents a binding site with a polymer residue and contains at least one cyano group in formula (300), and a solvent.

[0063] "Formula (300) contains at least one cyano group" means Ar, L 3 , T 3, R 3 This means that at least one of them has a cyano group.

[0064] The alkylene groups having 1 to 10 carbon atoms, alkenylene groups having 2 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms are as described above.

[0065] R 3 represents a monovalent organic group, and there are no particular restrictions as long as they do not impair the effects of the present invention, but examples include a cyano group or a group represented by the following formula. [ka] (In the above formula, *1 represents the bond portion to the aryl group having 6 to 40 carbon atoms. R2 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 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 alkyl groups having 1 to 10 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 10 carbon atoms.)

[0066] <polymer> The polymer comprises a compound (A) containing two or more epoxy groups and the following formula (301):

[0067] [ka] (In formula (301), R 2The first part represents a group that reacts with an epoxy group, U represents a group selected from the group consisting of halogen atoms, carboxyl groups, nitro groups, cyano groups, methylenedioxy groups, acetoxy groups, methylthio groups, amino groups, optionally substituted alkyl groups having 1 to 10 carbon atoms, optionally substituted alkenyl groups having 2 to 10 carbon atoms, optionally substituted alkoxy groups having 1 to 10 carbon atoms, and combinations thereof, m represents an integer from 0 to 5, D represents an arylene group or heterocycle having 6 to 40 carbon atoms, and L 1 This is synonymous with [1] above. It may be a reaction product with compound (B) represented by ).

[0068] Compound (A) containing two or more epoxy groups is as exemplified above as an epoxy group-containing compound.

[0069] The groups that are reactive with the epoxy group are as described above.

[0070] Specific examples of the optionally substituted alkyl groups having 1 to 10 carbon atoms, optionally substituted alkenyl groups having 2 to 10 carbon atoms, and optionally substituted alkoxy groups having 1 to 10 carbon atoms are as described above.

[0071] The arylene groups and heterocycles having 6 to 40 carbon atoms are as described above.

[0072] Specific examples of compounds containing two or more groups that are reactive with the epoxy group may be the compounds described below. [ka]

[0073] [ka]

[0074] The aforementioned polymer is given by the following formula (P): [ka] (In formula (P), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, Q 1 represents a divalent organic group, T 2 and T 3 Each of these independently represents a single bond, an ester bond, or an ether bond, L 2 and L 3 Each of the following independently represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted; D represents an arylene group or heterocycle having 6 to 40 carbon atoms; and U and m are the same as in [2] above. ) may be represented as .

[0075] The aforementioned Q 1 It may be derived from compound (A) containing two or more epoxy groups. Also, Q 1 This may be a substituted heterocyclic structure or a substituted arylene group having 6 to 40 carbon atoms. The definitions of each term are as described above.

[0076] <Solvent> The solvent used in the resist underlayer film forming composition of the present invention is not particularly limited as long as it is a solvent that can uniformly dissolve solid components such as the polymer at room temperature, but organic solvents commonly used in semiconductor lithography process chemicals are 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, cyclo Examples include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used individually or in combination of two or more.

[0077] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0078] <Acid Generator> As an optional component in the resist underlayer film forming composition of the present invention, either a thermal acid generator or a photoacid generator can be used, but the use of a thermal acid generator is preferred. 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 (pyridinium salt of p-phenolsulfonic acid), 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 hydroxybenzoic acid.

[0079] Examples of the photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0080] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0081] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0082] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0083] The aforementioned acid generating agent can be used by one type only, or by a combination of two or more types.

[0084] When the aforementioned acid generator is used, the content of the acid generator is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass, relative to the crosslinking agent described below.

[0085] <Crosslinking agent> Examples of crosslinking agents that may be included as optional components in the resist underlayer film forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (tetramethoxymethylglycoluryl) (POWDERLINK® 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.

[0086] Furthermore, the crosslinking agent of this application may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) that bond to a nitrogen atom in one molecule, as described in International Publication No. 2017 / 187969.

[0087] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule may be a glycoluryl derivative represented by the following formula (1E).

[0088] [ka] (In formula (1E), each of the four R1s independently represents a methyl group or an ethyl group, and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6).

[0089] [ka]

[0090] A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule can be 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).

[0091] [ka] (In formulas (2d) and (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.) The glycoluryl derivative represented by formula (1E) is obtained by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by formula (3d).

[0092] A nitrogen-containing compound having 2 to 6 substituents represented by formula (2d) in one molecule is, for example, a glycoluryl derivative represented by the following formula (2E).

[0093] [ka] (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.) Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0094] [ka] [ka]

[0095] With regard to nitrogen-containing compounds having 2 to 6 substituents represented by the following formula (1d) bonded to the aforementioned nitrogen atom in one molecule, the full disclosure in WO2017 / 187969 is incorporated herein by reference.

[0096] Furthermore, the above-mentioned 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.

[0097] [ka] (In the formula, Q 1 represents a single bond or an m1-valent organic group, and R 1 and R 4 each represent an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 each represent a hydrogen atom or a methyl group, and R 3 and R 6 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.) n1 represents an integer of 1 ≤ n1 ≤ 3, n2 represents an integer of 2 ≤ n2 ≤ 5, n3 represents an integer of 0 ≤ n3 ≤ 3, n4 represents an integer of 0 ≤ n4 ≤ 3, and 3 ≤ (n1 + n2 + n3 + n4) ≤ 6 represents an integer.) n5 represents an integer of 1 ≤ n5 ≤ 3, n6 represents an integer of 1 ≤ n6 ≤ 4, n7 represents an integer of 0 ≤ n7 ≤ 3, n8 represents an integer of 0 ≤ n8 ≤ 3, and 2 ≤ (n5 + n6 + n7 + n8) ≤ 5 represents an integer.) m1 represents an integer of 2 to 10.)

[0098] 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.)

[0099]

Chemical formula

[0100] The compounds represented by the above formulas (G-1) and (G-2) can be exemplified as follows.

[0101]

Chemical formula

[0102]

Chemical formula

[0103]

Chemical formula

[0104]

Chemical formula

[0105]

Chemical formula

[0106] The compounds represented by formulas (G-3) and (G-4) can be exemplified as follows.

[0107]

Chemical formula

[0108]

Chemical formula

[0109] The entire disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0110] When the crosslinking agent is used, the content ratio of the crosslinking agent is, for example, 1% to 50% by mass, preferably 5% to 30% by mass, based on the reaction product.

[0111] <Other components> The resist underlayer film-forming composition of the present invention does not produce pinholes or striations, and a surfactant can be added to further improve the coatability against surface unevenness. Examples of surfactants 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 fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink, Inc., product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added individually or in combination of two or more types.

[0112] The solid content of the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0113] <Underlying resist film> The resist underlayer film according to the present invention can be manufactured by applying the aforementioned resist underlayer film forming composition onto a semiconductor substrate and firing it.

[0114] Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention is coated include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0115] When using a semiconductor substrate with 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 films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho-Silicate Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0116] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0117] The thickness of the resist underlayer film formed can be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), or 0.005 μm (5 nm) to 0.05 μm. The ranges are m(50nm), 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), and 0.005μm(5nm). If the baking temperature is lower than the above range, crosslinking will be insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may decompose due to heat.

[0118] <Manufacturing method for patterned substrates, manufacturing method for semiconductor devices> The manufacturing process for patterned substrates involves the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist formed by coating and firing on the resist underlayer film using a known method is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, as well as resists containing metal elements. Examples include V146G from JSR Corporation, APEX-E from Cyprey Corporation, PAR710 from Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 from Shin-Etsu Chemical Co., Ltd. Additionally, examples include fluorine-containing polymer photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000).

[0119] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as those described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0120] Examples of resist compositions include the following compositions.

[0121] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by general formula (21).

[0122] [ka] In general formula (21), m represents an integer from 1 to 6.

[0123] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0124] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0125] L2 represents an alkylene group or single bond which may have substituents.

[0126] W1 represents a cyclic organic group which may have substituents.

[0127] M + This represents a cation.

[0128] 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 3rd to 7th periods of groups 3 to 15 of the periodic table.

[0129] 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) that includes an acid-dissociable group, and an acid generator.

[0130] [ka] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene with 6 to 20 carbon atoms. 1 R 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 groups are used. 1 They are the same or different. 2 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 This is a monovalent group having 1 to 20 carbon atoms that contains the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0131] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by formula (II), and structural units having acid-unstable groups, and an acid generator.

[0132] [ka] [In formula (II), R 2 X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. 1 These are single bonds, -CO-O-*, or -CO-NR 4 -* represents a bond with -Ar, and R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0133] Examples of resist films include the following:

[0134] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0135] [ka] (In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 1 and R 2 Each of these is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. 1 This is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. 2 (These are single bonds, ester bonds, or amide bonds.)

[0136] Examples of resist materials include the following:

[0137] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0138] [ka] (In equations (b1) and (b2), R A X is a hydrogen atom or a methyl group. 1 X is a single bond or an ester group. 2 X 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 portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X 2 At least one hydrogen atom in X 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 some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf4 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. 1 ~R 5 Each of these 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 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 sultone group, a sulfone group, or a sulfonium salt-containing group, and 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. 1 and R 2 These may combine to form a ring with the sulfur atom to which they are bonded.

[0139] A resist material comprising a base resin containing a polymer containing repeating units represented by the following formula (a).

[0140] [ka] (In formula (a), R A R is a hydrogen atom or a methyl group. 1 R is a hydrogen atom or an acid-unstable group. 2 This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. 2 (where m is -O-, -O-CH2-, or -NH-; where m is an integer from 1 to 4, and n is an integer from 0 to 3.) A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, It contains a base component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that is degradable in alkaline developer. The resist composition is characterized in that the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).

[0141] [ka] [In formula (f2-r-1), Rf 21 Each of these 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. * represents a bond.

[0142] The aforementioned 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).

[0143] [ka] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. X is a divalent linking group that does not have an acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have substituents. 01 R is a single bond or a divalent linking group. 2 These are, independently, organic groups that contain a fluorine atom.

[0144] Examples of coatings, coating solutions, and coating compositions include the following:

[0145] A coating comprising a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0146] An inorganic oxo / hydroxo-based composition.

[0147] A coating solution comprising an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, the first organometallic composition; and a hydrolyzable metal compound represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof), the coating solution comprising the hydrolyzable metal compound.

[0148] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0149] An inorganic pattern-forming precursor aqueous solution comprising a mixture of water, metal oxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing peroxide groups.

[0150] 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) lasers are used, but the resist underlayer forming composition of this application is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more preferably 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 the alkaline developer, for example, aqueous solutions of alkalis such as inorganic alkalis like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines like ethylamine and n-propylamine; secondary amines like diethylamine and di-n-butylamine; tertiary amines like triethylamine and methyldiethylamine; alcohol amines like dimethylethanolamine and triethanolamine; quaternary ammonium salts like tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines like pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, and more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate to develop the parts of the photoresist where the alkali dissolution rate has not improved. Through the above process, a substrate with the resist patterned can be manufactured.

[0151] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask. At this time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0152] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0153] The weight-average molecular weights of the polymers shown in the following synthesis examples and comparative synthesis examples in this specification are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions were as follows.

[0154] GPC column: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0155] <Synthesis Example A1> 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 9.60 g of 4-nitrocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.14 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 35.85 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A1 (compound A1). GPC analysis revealed that the obtained polymer A1 (compound A1) had a weight-average molecular weight of 860 on a standard polystyrene basis and a dispersion degree of 1.1. The structure present in polymer A1 (compound A1) is shown in the following formula. [ka]

[0156] <Synthesis example A2> 8.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 15.35 g of (E)-3-nitrocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.01 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 56.85 g of propylene glycol monomethyl ether in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A2 (compound A2). GPC analysis revealed that the obtained polymer A2 (compound A2) had a weight-average molecular weight of 1,140 on a standard polystyrene basis and a dispersion degree of 1.0. The structure present in polymer A2 (compound A2) is shown by the following formula. [ka]

[0157] <Synthesis example A3> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 4.76 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 45.68 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A3. GPC analysis revealed that the obtained polymer A3 had a weight-average molecular weight of 5,400 on a standard polystyrene basis and a dispersion degree of 3.4. The structure present in polymer A3 is shown by the following formula. [ka]

[0158] <Synthesis example A4> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 2.99 g of trans-p-coumaric acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.24 g of 4-nitrocinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 43.60 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A4. GPC analysis revealed that the obtained polymer A4 had a weight-average molecular weight of 2,800 on a standard polystyrene basis and a dispersion degree of 3.0. The structure present in polymer A4 is shown by the following formula. [ka]

[0159] <Synthesis example A5> In a reaction vessel, 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.13 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.66 g of 4-nitrocinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.73 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.16 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 62.70 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A5. GPC analysis revealed that the obtained polymer A5 had a weight-average molecular weight of 2,900 on a standard polystyrene basis and a dispersion degree of 2.4. The structure present in polymer A5 is shown by the following formula. [ka]

[0160] <Synthesis example A6> In a reaction vessel, 10.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.75 g of α-cyano-4-hydroxycinnamic acid (manufactured by Midori Chemical Co., Ltd.), 2.07 g of 4-nitrocinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.91 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.20 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 28.39 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A6. GPC analysis revealed that the obtained polymer A6 had a weight-average molecular weight of 2,700 on a standard polystyrene basis and a dispersion degree of 2.3. The structure present in polymer A6 is shown by the following formula. [ka]

[0161] <Synthesis example A7> In a reaction vessel, 9.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.77 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.45 g of terephthalaldehyde (manufactured by Tokyo Chemical Industries, Ltd.), and 0.82 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 39.76 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours. Subsequently, a solution of 0.64 g of malononitrile (manufactured by Junsei Chemical Co., Ltd.) dissolved in 1.50 g of propylene glycol monomethyl ether was added to the system, and the reaction was carried out for a further 4 hours to obtain a solution containing polymer A7. GPC analysis revealed that the obtained polymer A7 had a weight-average molecular weight of 3,900 on a standard polystyrene basis and a dispersion degree of 2.5. The structure present in polymer A7 is shown by the following formula.

[0162] [ka]

[0163] <Synthesis example A8> 6.00 g of diglycidyl terephthalate (manufactured by Nagase ChemteX Corporation, trade name: EX-711), 4.59 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.53 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 62.98 g of propylene glycol monomethyl ether in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A8. GPC analysis revealed that the obtained polymer A8 had a weight-average molecular weight of 5,400 on a standard polystyrene basis and a dispersion degree of 3.1. The structure present in polymer A8 is shown by the following formula.

[0164] [ka]

[0165] <Synthesis example A9> In a reaction vessel, 4.00 g of resorcinol diglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: EX-201), 3.74 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.43 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 46.27 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A9. GPC analysis revealed that the obtained polymer A9 had a weight-average molecular weight of 6,200 on a standard polystyrene basis and a dispersion degree of 4.3. The structure present in polymer A9 is shown by the following formula.

[0166] [ka]

[0167] <Synthesis Example A10> In a reaction vessel, 9.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.20 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.06 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.58 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 40.00 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A10. GPC analysis revealed that the obtained polymer A10 had a weight-average molecular weight of 3,900 on a standard polystyrene basis and a dispersion degree of 2.8. The structure present in polymer A10 is shown by the following formula.

[0168] [ka]

[0169] <Synthesis Example A11> In a reaction vessel, 15.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 4.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 26.48 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A11. GPC analysis revealed that the obtained polymer A11 had a weight-average molecular weight of 3,200 on a standard polystyrene basis and a dispersion degree of 2.3. The structure present in polymer A11 is shown by the following formula.

[0170] [ka]

[0171] <Synthesis Example A12> In a reaction vessel, 15.00 g of 30 wt% monomethyl diglycidyl isocyanuric acid PGME solution (manufactured by Shikoku Chemicals, Inc.), 4.90 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 28.87 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A12. GPC analysis revealed that the obtained polymer A12 had a weight-average molecular weight of 1,600 on a standard polystyrene basis and a dispersion degree of 2.3. The structure present in polymer A12 is shown by the following formula.

[0172] [ka]

[0173] <Synthesis Example A13> In a reaction vessel, 15.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.40 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.03 g of adamantanecarboxylic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 3.73 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A13. GPC analysis revealed that the obtained polymer A13 had a weight-average molecular weight of 3,500 on a standard polystyrene basis and a dispersion degree of 3.3. The structure present in polymer A13 is shown by the following formula.

[0174] [ka]

[0175] <Synthesis Example A14> In a reaction vessel, 15.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.40 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.22 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 5.52 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A13. GPC analysis revealed that the obtained polymer A13 had a weight-average molecular weight of 2,000 and a dispersion degree of 2.0 on a standard polystyrene basis. The structure present in polymer A13 is shown by the following formula.

[0176] [ka]

[0177] <Synthesis Example A15> In a reaction vessel, 15.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.40 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.10 g of 4-nitrocinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 27.67 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A15. GPC analysis revealed that the obtained polymer A15 had a weight-average molecular weight of 3,100 on a standard polystyrene basis and a dispersion degree of 2.4. The structure present in polymer A15 is shown by the following formula.

[0178] [ka]

[0179] <Synthesis example A16> In a reaction vessel, 15.00 g of 30 wt% PGME solution of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.40 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.64 g of tetrabromophthalic anhydride (manufactured by Tokyo Chemical Industries, Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 6.15 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A16. GPC analysis revealed that the obtained polymer A16 had a weight-average molecular weight of 2,300 on a standard polystyrene basis and a dispersion degree of 1.9. The structure present in polymer A16 is shown by the following formula.

[0180] [ka]

[0181] <Synthesis Example A17> In a reaction vessel, 15.00 g of 30 wt% monomethyl diglycidyl isocyanuric acid PGME solution (manufactured by Shikoku Chemicals, Inc.), 3.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.97 g of adamantanecarboxylic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 25.94 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A17. GPC analysis revealed that the obtained polymer A17 had a weight-average molecular weight of 1,300 on a standard polystyrene basis and a dispersion degree of 2.3. The structure present in polymer A17 is shown by the following formula.

[0182] [ka]

[0183] <Synthesis Example A18> In a reaction vessel, 12.00 g of 30 wt% monomethyl diglycidyl isocyanuric acid PGME solution (manufactured by Shikoku Chemicals, Inc.), 2.41 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.23 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 25.97 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A18. GPC analysis revealed that the obtained polymer A18 had a weight-average molecular weight of 1,600 on a standard polystyrene basis and a dispersion degree of 2.2. The structure present in polymer A18 is shown by the following formula.

[0184] [ka]

[0185] <Synthesis Example A19> In a reaction vessel, 15.00 g of 30 wt% monomethyl diglycidyl isocyanuric acid PGME solution (manufactured by Shikoku Chemicals, Inc.), 3.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.49 g of tetrabromophthalic anhydride (manufactured by Tokyo Chemical Industries, Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 32.02 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer A19. GPC analysis revealed that the obtained polymer A19 had a weight-average molecular weight of 2,000 and a dispersion degree of 2.1 on a standard polystyrene basis. The structure present in polymer A19 is shown by the following formula.

[0186] [ka]

[0187] <Comparative Synthesis Example A1> 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were dissolved in 682.00 g of propylene glycol monomethyl ether in a reaction vessel. After purging the reaction vessel with nitrogen, the mixture was reacted at 130°C for 24 hours to obtain a solution containing comparative polymer A1. GPC analysis revealed that the obtained comparative polymer A1 had a weight-average molecular weight of 6,800 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer A1 is shown by the following formula. [ka]

[0188] <Comparative synthesis example A2> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.74 g of isophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 41.62 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing comparative polymer A2. GPC analysis revealed that the obtained comparative polymer A2 had a weight-average molecular weight of 7,600 on a standard polystyrene basis and a dispersion degree of 5.6. The structure present in comparative polymer A2 is shown by the following formula. [ka]

[0189] <Comparative synthesis example A3> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 4.10 g of isophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 43.06 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing comparative polymer A3. GPC analysis revealed that the obtained comparative polymer A3 had a weight-average molecular weight of 7,400 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer A3 is shown by the following formula. [ka]

[0190] <Comparative synthesis example A4> 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.68 g of 5-methoxyisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.10 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 36.94 g of propylene glycol monomethyl ether in a reaction vessel. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing comparative polymer A4. GPC analysis revealed that the obtained comparative polymer A4 had a weight-average molecular weight of 7,300 on a standard polystyrene basis and a dispersion degree of 5.2. The structure present in comparative polymer A4 is shown by the following formula. [ka]

[0191] (Preparation of the resist underlayer film) (Examples, Comparative Examples) The polymers (compounds), crosslinking agents, curing catalysts (acid generators), and solvents obtained in the above synthesis examples A1 to A19 and comparative synthesis examples A1 to A4 were mixed in the proportions shown in Tables A1 and A2, and the mixtures were filtered through a fluororesin filter with a pore size of 0.1 μm to prepare solutions of the resist underlayer film forming compositions.

[0192] In Tables A1 and A2, tetramethoxymethyl glycoluryl is abbreviated as PL-LI, imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, surfactant as R-30N, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amount of each additive is shown in parts by mass.

[0193] [Table 1]

[0194] [Table 2]

[0195] (Elution test into photoresist solvent) Each of the resist underlayer-forming compositions of Examples A1-A19 and Comparative Examples A1-A4 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is the solvent used for photoresists. A film thickness change of less than 5 Å was considered good, and a change of 5 Å or more was considered poor. The results are shown in Table A3.

[0196] [Table 3]

[0197] (Resistance patterning evaluation) [Test of resist pattern formation using electron beam lithography equipment] A resist underlayer-forming composition was applied to 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 underlayer with a thickness of 5 nm. An EUV positive-type resist solution was spin-coated onto the resist underlayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed to electron beam lithography (ELS-G130) under predetermined conditions. After exposure, it was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle developed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. The photoresist patterns obtained in this manner were evaluated for the feasibility of forming 22 nm line-and-space (L / S) patterns. 22 nm L / S pattern formation was confirmed in all cases of Examples A1 to A19. In Comparative Example A3, 22 nm L / S pattern formation could not be confirmed. Furthermore, the optimal irradiation energy was defined as the charge amount required to form a 22 nm line / 44 nm pitch (line-and-space (L / S=1 / 1)), and the irradiation energy at that time (μC / cm²) was evaluated. 2 Table A4 shows the minimum CD size and LWR at which no collapse is observed within the resist pattern shot. Examples A1 to A19 showed improvements in LWR and minimum CD size compared to comparative examples A1 to A4.

[0198] [Table 4]

[0199] <Synthesis Example B1> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 2.99 g of trans-p-coumaric acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.95 g of trans-cinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 42.44 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer B1. GPC analysis revealed that the obtained polymer B1 had a weight-average molecular weight of 2,900 on a standard polystyrene basis and a dispersion degree of 2.3. The structure present in polymer B1 is shown by the following formula. [ka]

[0200] <Synthesis example B2> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 2.99 g of trans-p-coumaric acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.04 g of 4-methylcinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 42.44 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer B2. GPC analysis revealed that the obtained polymer B2 had a weight-average molecular weight of 3,000 on a standard polystyrene basis and a dispersion degree of 2.2. The structure present in polymer B2 is shown by the following formula. [ka]

[0201] <Synthesis Example B3> In a reaction vessel, 35.00 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene propylene glycol monomethyl ether solution (DIC Corporation, product name WR-400), 1.99 g of 5,5-diethylbarbituric acid (Tateyama Chemicals, Inc.), 0.57 g of trans-cinnamic acid (Tokyo Chemical Industries, Ltd.), and 0.32 g of tetrabutylphosphonium bromide (Hokko Chemical Industry Co., Ltd.) were added to 5.10 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer B3. GPC analysis revealed that the obtained polymer B3 had a weight-average molecular weight of 3,700 on a standard polystyrene basis and a dispersion degree of 2.1. The structure present in polymer B3 is shown by the following formula. [ka]

[0202] <Synthesis example B4> 6.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 8.71 g of trans-cinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.76 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.16 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 36.48 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B4 (compound B4). GPC analysis revealed that the obtained polymer B4 (compound B4) had a weight-average molecular weight of 680 on a standard polystyrene basis and a dispersion degree of 1.1. The structure present in polymer B4 (compound B4) is shown by the following formula. [ka]

[0203] <Synthesis Example B5> 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 8.06 g of 4-methylcinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.14 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 32.26 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B5 (compound B5). GPC analysis revealed that the obtained polymer B5 (compound B5) had a weight-average molecular weight of 760 on a standard polystyrene basis and a dispersion degree of 1.1. The structure present in polymer B5 (compound B5) is shown by the following formula. [ka]

[0204] <Synthesis example B6> 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 8.90 g of trans-4-methoxycinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.14 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 34.23 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B6 (compound B6). GPC analysis revealed that the obtained polymer B6 (compound B6) had a weight-average molecular weight of 760 on a standard polystyrene basis and a dispersion degree of 1.0. The structure present in polymer B6 (compound B6) is shown by the following formula. [ka]

[0205] <Synthesis Example B7> 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 8.25 g of 4-fluorocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.14 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 32.72 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B7 (compound B7). GPC analysis revealed that the obtained polymer B7 (compound B7) had a weight-average molecular weight of 810 on a standard polystyrene basis and a dispersion degree of 1.0. The structure present in polymer B7 (compound B7) is shown by the following formula. [ka]

[0206] <Comparative Synthesis Example B1> 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemicals, Inc.), and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the mixture was reacted at 130°C for 24 hours to obtain a solution containing comparative polymer B1. GPC analysis revealed that the obtained comparative polymer B1 had a weight-average molecular weight of 6,800 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer B1 is shown by the following formula. [ka]

[0207] <Comparative synthesis example B2> In a reaction vessel, 40.00 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene propylene glycol monomethyl ether solution (DIC Corporation, trade name: WR-400), 2.87 g of trans-p-coumaric acid (Tokyo Chemical Industries, Ltd.), 0.37 g of tetrabutylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 0.08 g of hydroquinone (Tokyo Chemical Industries, Ltd.) were added to 5.95 g of propylene glycol monomethyl ether and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing comparative polymer B2. GPC analysis revealed that the obtained comparative polymer B2 had a weight-average molecular weight of 6,200 on a standard polystyrene basis and a dispersion degree of 3.0. The structure present in comparative polymer B2 is shown by the following formula. [ka]

[0208] (Preparation of the resist underlayer film) (Examples, Comparative Examples) The polymers (compounds), crosslinking agents, curing catalysts, and solvents obtained in the above synthesis examples B1-B7 and comparative synthesis examples B1-B2 were mixed in the proportions shown in Tables B1 and B2, and the mixtures were filtered through a fluororesin filter with a pore size of 0.1 μm to prepare solutions of the resist underlayer film forming compositions. In Tables B1 and B2, tetramethoxymethyl glycoluryl is abbreviated as PL-LI, imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, surfactant as R-30N, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amount of each additive is shown in parts by mass.

[0209] [Table 5]

[0210] [Table 6]

[0211] (Elution test into photoresist solvent) Each of the resist underlayer-forming compositions of Examples B1-B7 and Comparative Examples B1-B2 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is the solvent used for photoresists. A film thickness change of less than 5 Å was considered good, and a change of 5 Å or more was considered poor. The results are shown in Table B3.

[0212] [Table 7]

[0213] (Resistance patterning evaluation) [Test of resist pattern formation using electron beam lithography equipment] A resist underlayer-forming composition was applied to 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 underlayer with a thickness of 5 nm. An EUV positive-type resist solution was spin-coated onto the resist underlayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed to electron beam lithography (ELS-G130) under predetermined conditions. After exposure, it was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle developed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. The photoresist patterns obtained in this manner were evaluated for the feasibility of forming 22 nm line-and-space (L / S) patterns. 22 nm L / S pattern formation was confirmed in all cases of Examples B1 to B7. Furthermore, the optimal irradiation energy was defined as the charge amount required to form a 22 nm line / 44 nm pitch (line-and-space (L / S=1 / 1)), and the irradiation energy at that time (μC / cm²) was evaluated. 2 Table B4 shows the values ​​for ), and LWR. In all of Examples B1 to B7, an improvement in LWR was observed compared to Comparative Examples B1 to B2.

[0214] [Table 8]

[0215] <Synthesis example C1> In a reaction vessel, 9.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.77 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 1.45 g of terephthalaldehyde (manufactured by Tokyo Chemical Industries, Ltd.), and 0.82 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 39.76 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours. Subsequently, a solution of 0.64 g of malononitrile (manufactured by Junsei Chemical Co., Ltd.) dissolved in 1.50 g of propylene glycol monomethyl ether was added to the system, and the reaction was carried out for a further 4 hours to obtain a solution containing polymer C1. GPC analysis revealed that the obtained polymer C1 had a weight-average molecular weight of 3,900 on a standard polystyrene basis and a dispersion degree of 2.5. The structure present in polymer C1 is shown by the following formula. [ka]

[0216] <Synthesis Example C2> In a reaction vessel, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.79 g of 3-cyanobenzoic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 37.81 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer C2. GPC analysis revealed that the obtained polymer C2 had a weight-average molecular weight of 3,300 on a standard polystyrene basis and a dispersion degree of 2.4. The structure present in polymer C2 is shown by the following formula. [ka]

[0217] <Synthesis Example C3> In a reaction vessel, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.93 g of α-cyanocinnamic acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.10 g of hydroquinone (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 38.76 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer C3. GPC analysis revealed that the obtained polymer C3 had a weight-average molecular weight of 2,900 and a dispersion degree of 2.3 on a standard polystyrene basis. The structure present in polymer C3 is shown by the following formula. [ka]

[0218] <Comparative Synthesis Example C1> 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemicals, Inc.), and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether and dissolved in a reaction vessel. After purging the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing comparative polymer C1. GPC analysis revealed that the obtained comparative polymer C1 had a weight-average molecular weight of 6,800 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer C1 is shown by the following formula. [ka]

[0219] <Comparative Synthesis Example C2> In a reaction vessel, 12.86 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Corporation), 9.67 g of terephthalaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.87 g of 4-hydroxybenzaldehyde (manufactured by Junsei Chemical Co., Ltd.), and 1.09 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 125.96 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 135°C for 6 hours. Subsequently, a solution of 8.51 g of malononitrile (manufactured by Junsei Chemical Co., Ltd.) dissolved in 34.04 g of propylene glycol monomethyl ether was added to the system, and the reaction was carried out for a further 2 hours to obtain a solution containing comparative polymer C2 (comparative compound C2). GPC analysis revealed that the obtained comparative polymer C2 (comparative compound C2) had a weight-average molecular weight of 980 and a dispersion degree of 1.3 on a standard polystyrene basis. The structure present in comparative polymer C2 (comparative compound C2) is shown by the following formula. [ka] (L1 represents the connection point with L2 and L3)

[0220] (Preparation of the resist underlayer film) (Examples, Comparative Examples) The polymers (compounds), crosslinking agents, curing catalysts, and solvents obtained in the above synthesis examples C1-C3 and comparative synthesis examples C1-C2 were mixed in the proportions shown in Tables C1 and C2, and the mixtures were filtered through a fluororesin filter with a pore size of 0.1 μm to prepare solutions of the resist underlayer film forming compositions. In Tables C1 and C2, tetramethoxymethyl glycoluryl is abbreviated as PL-LI, imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, surfactant as R-30N, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amount of each additive is shown in parts by mass.

[0221] [Table 9]

[0222] [Table 10]

[0223] (Elution test into photoresist solvent) Each of the resist underlayer-forming compositions of Examples C1-C3 and Comparative Examples C1-C2 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is the solvent used for photoresists. A film thickness change of less than 1 Å was considered good, and a change of 1 Å or more was considered poor. The results are shown in Table C3.

[0224] [Table 11]

[0225] (Resistance patterning evaluation) [Test of resist pattern formation using electron beam lithography equipment] A resist underlayer-forming composition was applied to 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 underlayer with a thickness of 5 nm. An EUV positive-type resist solution was spin-coated onto the resist underlayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed to electron beam lithography (ELS-G130) under predetermined conditions. After exposure, it was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle developed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. The photoresist patterns obtained in this manner were evaluated for the feasibility of forming 22 nm line-and-space (L / S) patterns. 22 nm L / S pattern formation was confirmed in all cases of Examples C1 to C3. Furthermore, the optimal irradiation energy was defined as the charge amount required to form a 22 nm line / 44 nm pitch (line-and-space (L / S=1 / 1)), and the irradiation energy at that time (μC / cm²) was evaluated. 2 Table C4 shows the minimum CD size and LWR at which no collapse is observed within the resist pattern shot. Examples C1 to C3 showed improvements in LWR and minimum CD size compared to Comparative Example C1.

[0226] [Table 12] [Industrial applicability]

[0227] The resist underlayer film forming composition according to the present invention provides a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for manufacturing a substrate with a resist pattern using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

Claims

1. A resist underlayer film forming composition comprising a polymer and a solvent, The aforementioned polymer is given by the following formula (P1): 【Chemistry 1】 (In formula (P1), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; Q1 represents a divalent organic group containing a heterocyclic structure in the main chain; T2 and T3 each independently represent a single bond, an ester bond, or an ether bond; L2 and L3 each independently represent a single bond or an alkenylene group having 2 to 10 carbon atoms, which may be substituted with a cyano group; U represents a nitro group; D represents benzene, naphthalene, or anthracene; and n represents an integer from 0 to 3.) The following formula (103): 【Chemistry 2】 (In formula (103), Ar represents an aromatic ring having 6 to 40 carbon atoms, which may be substituted, L １ A resist underlayer film forming composition comprising a structure represented by ( ) at the polymer end, where is a single bond, ester bond, ether bond, alkylene group having 1 to 2 carbon atoms, or alkenylene group having 2 to 3 carbon atoms, and n is an integer from 1 to 3.

2. The resist underlayer film forming composition according to claim 1, wherein the polymer is a reaction product of a compound (A) containing two epoxy groups and a compound (B) containing two groups that are reactive with the epoxy groups.

3. The resist underlayer forming composition according to claim 2, wherein the compound (A) comprises a heterocyclic structure.

4. The resist underlayer forming composition according to claim 3, wherein the compound (A) comprises a heterocyclic structure selected from the group consisting of furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthlene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineone, triazinedione, and triazinetrione.

5. The resist underlayer film forming composition according to claim 2, wherein the compound (A) containing two epoxy groups is selected from the following formula. 【Transformation 3】

6. The resist underlayer film forming composition according to claim 2, wherein compound (B), which contains two groups that are reactive with the epoxy group, comprises an aromatic ring structure selected from the group consisting of benzene, naphthalene, and anthracene.

7. A resist underlayer film forming composition according to any one of claims 1 to 6, further comprising an acid generator.

8. A resist underlayer film forming composition according to any one of claims 1 to 7, further comprising a crosslinking agent.

9. A resist underlayer film characterized by being a fired product of a coated film made from the resist underlayer film forming composition described in any one of claims 1 to 8.

10. A step of forming a resist underlayer film by applying a resist underlayer film forming composition according to any one of claims 1 to 8 onto a semiconductor substrate and baking it, A step of forming a resist film by coating the resist on the resist underlayer film and baking it. A step of exposing the resist underlayer film and the semiconductor substrate coated with the resist, The process of developing and patterning the resist film after exposure. A method for manufacturing patterned substrates, including [the specified method].

11. A step of forming a resist underlayer on a semiconductor substrate, comprising the resist underlayer forming composition according to any one of claims 1 to 8, A step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following:

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