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] The present invention relates to a composition used in lithography processes in semiconductor manufacturing, particularly in cutting-edge lithography processes (ArF, EUV, EB, etc.), and also to a method for producing a substrate with a resist pattern using the resist underlayer film, and a method for producing a semiconductor device. [Background technology]

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the thin film with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern. In recent years, the integration density of semiconductor devices has increased, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical use of EUV light (wavelength 13.5 nm) or EB (electron beam) has been considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to influences from the semiconductor substrate and other factors has become a major problem. To address this issue, methods for providing a resist underlayer film between the resist and the semiconductor substrate have been widely investigated. Patent Document 1 discloses a resist underlayer film-forming composition for EUV lithography containing a condensation polymer. Patent Document 2 discloses a resist underlayer film-forming composition containing a polymer having a specific unit structure in the 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 Application Laid-Open No. 2015-145944 [Patent Document 3] International Patent Application Publication No. 2019 / 059202 Summary of the Invention [Problem to be solved by the invention]

[0004] The properties required for the resist underlayer film include, for example, that it does not intermix with the resist film formed on top (that is, it is insoluble in a resist solvent) and that it has a faster dry etching rate than 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 thinner than conventional films. When forming such a thin film, 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, when forming a resist pattern, in a negative development process in which the unexposed portions of the resist film are removed using a solvent capable of dissolving the resist film, usually an organic solvent, in the development step, leaving the exposed portions of the resist film as a resist pattern, or in a positive development process in which the exposed portions of the resist film are removed, leaving the unexposed portions of the resist film as a resist pattern, improving the adhesion of the resist pattern is a major issue.

[0007] There is also a demand for suppressing deterioration of LWR (Line Width Roughness) during resist pattern formation, forming resist patterns with good rectangular shapes, and improving resist sensitivity.

[0008] An object of the present invention is to provide a composition for forming a resist underlayer film that can solve the above-mentioned problems and that can form a desired resist pattern, and a method for forming a resist pattern that uses the resist underlayer film-forming composition. [Means for solving the problem]

[0009] The present invention encompasses the following. [1] The following formula (100): [ka] (In formula (100), Ar represents an optionally substituted aromatic ring group having 6 to 40 carbon atoms; 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 each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group; n represents an integer of 0 to 5, * represents a bonding portion to a polymer or compound residue. A resist underlayer film-forming composition comprising a polymer or compound having a structure represented by the formula: [2] A compound containing a partial structure represented by formula (100) and a solvent, In equation (100), Ar represents an optionally substituted aromatic ring having 6 to 40 carbon atoms; 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 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 from 1 to 3 The resist underlayer film forming composition according to [1]. [3] The compound is a compound represented by the following formula (101): [ka] (In formula (101), R 1 represents a group reactive with an epoxy group, Ar, L 1 and n is Ar and L in [2] 0 and n are synonymous with each other. [4] A resist underlayer film-forming composition comprising a polymer and a solvent, The following formula (103): [ka] In formula (103), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 1 represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms, and n represents an integer of 1 to 3. [5] A compound containing two or more epoxy groups and a compound represented by the following formula (102): [ka] (In formula (102), R 1represents a group reactive with an epoxy group, D represents an aromatic ring or heterocycle having 6 to 40 carbon atoms, L 1 and n is L in [2] 0 and n are synonymous with each other. 1. A resist underlayer film-forming composition comprising a polymer obtained by reacting a compound represented by the formula (I) with a solvent. [6] The resist underlayer film forming composition according to [5], wherein the polymer contains the structure represented by the formula (103) at a polymer terminal. [7] A polymer represented by the following formula (P1): [ka] (In formula (P1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 represents a divalent organic group, and T 2 and T 3 each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3 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, U represents a nitro group, D represents an aromatic ring or heterocycle having 6 to 40 carbon atoms, and n represents an integer of 0 to 3, and a solvent. [8] The epoxy group-containing compound, the compound containing two or more epoxy groups, or Q 1 The resist underlayer film forming composition according to [3], [5] or [7], wherein the compound (I) contains a heterocyclic structure. [9] Said L 1 ~L 3 The resist underlayer film forming composition according to any one of [2] to [8], wherein at least one of the groups is an alkenylene group having 2 to 10 carbon atoms.

[10] The following formula (200): [ka] In formula (200), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 2 represents an optionally substituted alkenylene group having 2 to 10 carbon atoms, and n R 2 each independently represents 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 of 1 to 10 carbon atoms, and an optionally substituted alkoxy group of 1 to 10 carbon atoms, n represents an integer of 0 to 5, and * represents a bonding moiety to a polymer or compound residue. A resist underlayer film forming composition comprising: a polymer or compound containing at its terminal a structure represented by the following formula (I):

[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 reactive with the epoxy groups, The resist underlayer film forming composition according to

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

[12] The polymer has the following formula (P2): [ka] (In formula (P2), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 and Q 2 each independently represents a divalent organic group containing a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms; T 2 and T 3 each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3each 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.

[13] The following formula (300): [ka] In formula (300), Ar represents an optionally substituted aryl group having 6 to 40 carbon atoms, and L 3 represents a single bond, an ester bond or an ether bond, and T 3 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, and n R 3 each independently represents a monovalent organic group, and n represents an integer of 0 to 5. * represents a bonding moiety to a polymer residue, and contains at least one cyano group in formula (300).

[14] The polymer has the following formula (P3): [ka] (In formula (P3), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 represents a divalent organic group, and T 2 and T 3 each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3each independently represent a single bond, an optionally substituted alkylene group of 1 to 10 carbon atoms, or an optionally substituted alkenylene group of 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 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 of 1 to 10 carbon atoms, an optionally substituted alkenyl group of 2 to 10 carbon atoms, and an optionally substituted alkoxy group of 1 to 10 carbon atoms; and m represents an integer of 0 to 5.

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

[14] , further comprising an acid generator.

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

[15] , further comprising a crosslinking agent.

[17]

[16] A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of [1] to

[16] .

[18] a step of applying the resist underlayer film-forming composition according to any one of [1] to

[16] onto a semiconductor substrate and baking the composition to form a resist underlayer film; a step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

[19] forming a resist underlayer film on a semiconductor substrate, the resist underlayer film being composed of the resist underlayer film-forming composition according to any one of [1] to

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

[0010] The resist underlayer film forming composition of the present invention has excellent coatability onto semiconductor substrates to be processed and excellent adhesion at the interface between the resist and the resist underlayer film during resist pattern formation, preventing peeling of the resist pattern and suppressing deterioration of LWR (line width roughness) during resist pattern formation, enabling the resist pattern size (minimum CD size) to be minimized and forming a good rectangular resist pattern. This effect is particularly pronounced when using EUV (wavelength 13.5 nm) or EB (electron beam). DETAILED DESCRIPTION OF THE INVENTION

[0011] <Resist Underlayer Film-Forming Composition> The resist underlayer film-forming composition of the present invention is represented by the following formula (100): [ka] (In formula (100), Ar represents an optionally substituted aromatic ring group having 6 to 40 carbon atoms; 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 each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group; n represents an integer of 0 to 5, * represents a bonding portion to the polymer or compound residue. ) and a solvent are included.

[0012] Examples of the aromatic ring 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. Of these, benzene, naphthalene, and anthracene are preferred.

[0013] Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, a m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, a m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0014] Examples of the arylene group having 6 to 40 carbon atoms include a phenylene group, an o-methylphenylene group, an m-methylphenylene group, a p-methylphenylene group, an o-chlorophenylene group, an m-chlorophenylene group, a p-chlorophenylene group, an o-fluorophenylene group, a p-fluorophenylene group, an o-methoxyphenylene group, a p-methoxyphenylene group, a p-nitrophenylene group, a p-cyanophenylene group, an α-naphthylene group, a β-naphthylene group, an o-biphenylylene group, an m-biphenylylene group, a p-biphenylylene group, a 1-anthrylene group, a 2-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group, a 2-phenanthrylene group, a 3-phenanthrylene group, a 4-phenanthrylene group, and a 9-phenanthrylene group.

[0015] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 1-ethyl-n-propylene group. propylene, cyclopentylene, 1-methylcyclobutylene, 2-methylcyclobutylene, 3-methylcyclobutylene, 1,2-dimethylcyclopropylene, 2,3-dimethylcyclopropylene, 1-ethylcyclopropylene, 2-ethylcyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene , 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 cyclobutylene group, 3-ethylcyclobutylene group, 1,2-dimethylcyclobutylene group, 1,3-dimethylcyclobutylene group, 2,2-dimethylcyclobutylene group, 2,3-dimethylcyclobutylene group, 2,4-dimethylcyclobutylene group, 3,3-dimethylcyclobutylene group, 1-n-propylcyclopropylene group, 2-n-propylcyclopropylene group, 1-isopropylcyclopropylene group, 2-isopropylcyclopropylene group, 1,2,2-trimethylcyclopropylene group, 1,2,3-trimethylcyclopropylene group, 2,2,Examples of the cyclopropylene group include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0016] Examples of the alkenylene group having 2 to 10 carbon atoms include the alkylene groups having 2 to 10 carbon atoms, which have at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms. Of the alkenylene groups having 2 to 10 carbon atoms, a vinylene group is preferred.

[0017] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0018] The term "optionally 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 hydroxy 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] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group. 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, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, and a decyl group. Therefore, examples of the alkenyl group having 2 to 10 carbon atoms include the aforementioned alkyl groups having 2 to 10 carbon atoms, which have at least one double bond formed by removing hydrogen atoms from adjacent carbon atoms.

[0020] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n n-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 comprises A compound containing a partial structure represented by formula (100) and a solvent, In equation (100), Ar represents an optionally substituted aromatic ring having 6 to 40 carbon atoms; L 0 represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, T 0 represents a single bond, n R 0 each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group; n represents an integer from 1 to 3 The resist underlayer film-forming composition A is included.

[0022] The compound is a compound represented by the following formula (101): [ka] (In formula (101), R 1 represents a group reactive with an epoxy group, and Ar, L 1 and n is Ar and L in the above formula (100). 0 Ar is synonymous with n, and preferably represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 1 represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms, and n represents an integer of 1 to 3.

[0023] The group (R 1 ) include a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group, and among these, a hydroxy group or a carboxy group is preferred from the viewpoint of reactivity with an epoxy group.

[0024] Examples of the epoxy group-containing compound include the following. [ka] [ka] [ka]

[0025] Examples of the compound represented by the above formula (101) include the following. [ka] [ka]

[0026] The lower limit of the weight average molecular weight of the compound 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 (Containing Polymer)> The resist underlayer film forming composition of the present invention contains a polymer and a solvent, and may contain the structure represented by the above formula (100) at the terminal of the polymer.

[0028] (polymer) The polymer (copolymer, resin) contained in the resist underlayer film-forming composition of the present invention is not limited as long as it exhibits the effects of the present invention, and may be, for example, a polymer having the following structure described in WO2009 / 008446: [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 of 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 the following formula:

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

[0030] Furthermore, it may be a polymer having the following structure as described in WO2013 / 018802:

[0031] Formula (1a): [ka] [In the formula, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 represents a group represented by 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 an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, a carboxyl 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 a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms; Q represents a group represented by formula (5) or (6): [ka] (wherein Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the alkylene group, phenylene group, naphthylene group, and anthrylene group are each optionally substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxy group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group consisting of a combination thereof; n1 and n2 each represent the number 0 or 1; and X2 represents formula (2), formula (3), or formula (0)).

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

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

[0034] [ka] (In formulas (1-1) and (1-2), R 1 and R 2 each 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 each independently represent 0 or 1; and two Qs each represent a single bond, an -O- group, or a -C(=O)-O- group, provided that when both i and j are 0, at least one of the two Qs represents a -C(=O)-O- group. For example, the resin may be a compound represented by the following formula (A): [ka] (In formula (A), R 1 , i and j have the same meanings as above, and at least one compound represented by the following formula (B): [ka] (In formula (B), R 2 and Q have the same meanings as above. A copolymer with at least one diepoxy compound represented by the following formula (I) can be used.

[0035] That is, at least one compound represented by formula (A) and at least one diepoxy compound represented by formula (B) are dissolved in an organic solvent in an appropriate molar ratio, and polymerized, if necessary, in the presence of a catalyst, to obtain a copolymer having a repeating structural unit represented by formula (1-1) and a repeating structural unit represented by formula (1-2).

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

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

[0038] Examples of the copolymer having the repeating structural unit represented by the above formula (1-1) and the repeating structural unit represented by the following formula (1-2) include copolymers having repeating structural units represented by the following formulas (1a) to (1n). [ka] [ka]

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

[0040] The polymer comprises a compound containing two or more epoxy groups and a compound represented by the following formula (102): [ka] (In formula (102), R 1 represents a group reactive with an epoxy group, D represents an arylene group or a heterocycle having 6 to 40 carbon atoms, L 1 and n is L in the above formula (100). 0 and n, and preferably L 1 represents an optionally substituted alkenylene group having 2 to 10 carbon atoms, and n R 1 are independently 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, and n is an integer of 0 to 5.

[0041] The compound containing two or more epoxy groups is as described above.

[0042] Examples of the heterocycle 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, triazineone, triazinedione, and triazinetrione. Among these, triazineone, 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): [ka] (In formula (P), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 represents a divalent organic group, and T 2 and T 3 each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3 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, U represents a hydrogen atom or a nitro group, D represents an aromatic ring or heterocycle having 6 to 40 carbon atoms, and n represents an integer of 1 to 3.) The meaning and specific examples of each term are as described above.

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

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

[0047] Of 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, for example, as described in 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 has the following formula (200): [ka] In formula (200), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L 2 represents an optionally substituted alkenylene group having 2 to 10 carbon atoms, and n R 2 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 of 1 to 10 carbon atoms, and an optionally substituted alkoxy group of 1 to 10 carbon atoms, n represents an integer of 0 to 5, and * represents a bonding moiety to a polymer or compound residue.

[0050] R 2 is preferably three or less 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 groups.

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

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

[0055] [ka] [ka]

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

[0057] The heterocyclic structure is as described above.

[0058] The heterocyclic structure may be a structure derived from barbituric acid.

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

[0060] The polymer has the following formula (P): [ka] (In formula (P), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 and Q 2 each independently represents a divalent organic group containing a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms; T 2 and T 3each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3 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.) Each term is as defined above.

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

[0062] <Resist Underlayer Film Forming Composition C> The resist underlayer film-forming composition of the present invention has the following formula (300): [ka] In formula (300), Ar represents an optionally substituted aryl group having 6 to 40 carbon atoms, and L 3 represents a single bond, an ester bond or an ether bond, and T 3 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, and n R 3 each independently represents a monovalent organic group, and n represents an integer of 0 to 5. * represents a bonding moiety to a polymer residue, and contains at least one cyano group in formula (300).

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

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

[0065] R 3 represents a monovalent organic group, and is not particularly limited as long as it does not impair the effects of the present invention. Examples thereof include a cyano group or a group represented by the following formula: [ka] (In the above formula, *1 represents a bonding site 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 an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 10 carbon atoms.)

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

[0067] [ka] (In formula (301), R 2represents a group reactive with an epoxy group; U represents a group selected from the group consisting of 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, an optionally substituted alkenyl group having 2 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms, and combinations thereof; m represents an integer of 0 to 5; D represents an arylene group or heterocycle having 6 to 40 carbon atoms; L 1 has the same meaning as the above [1].

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

[0069] The group reactive with the epoxy group is as described above.

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

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

[0072] Specific examples of the compound containing two or more groups reactive with an epoxy group include the compounds described below. [ka]

[0073] [ka]

[0074] The polymer has the following formula (P): [ka] (In formula (P), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 represents a divalent organic group, and T 2 and T 3 each independently represents a single bond, an ester bond, or an ether bond; L 2 and L 3 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, and U and m are as defined in [2] above.

[0075] Q 1 may be derived from the compound (A) containing two or more epoxy groups. 1 may be an optionally substituted heterocyclic structure or an optionally 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 can uniformly dissolve the components contained therein that are solid at room temperature, such as the polymer, but organic solvents generally used in chemical solutions for semiconductor lithography processes 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, cyclohexane, cyclohexane-1, cyclohexane-2, cyclohexane-3, cyclohexane-4, cyclohexane-5, cyclohexane-6, cyclohexane-7, cyclohexane-8, cyclohexane-9, cyclohexane-10, cyclohexane-11, cyclohexane-12, cyclohexane-13, cyclohexane-14, cyclohexane-15, cyclohexane-16, cyclohexane-17, cyclohexane-18, cyclohexane-19, cyclohexane-20, cyclohexane-21, cyclohexane-22, cyclohexane-23, cyclohexane-24, cyclohexane-25, cyclohexane-26, cyclohexane-27, cyclohexane-28, cyclohexane-29, cyclohexane-30, cyclohexane-31, cyclohexane-32, cyclohexane-33, cyclohexane-34, cyclohexane-35, cyclohexane-36, cyclohexane-37, cyclohexane-38, cyclohexane-49, cyclohexane-49, cyclohexane-51, cyclohexane-52, cyclohexane-19, cyclohexane-19, cyclohexane-29, cyclohexane-19, cyclohexane-29, cyclo Examples of suitable solvents 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 may be used alone 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, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being particularly preferred.

[0078] <Acid generator> The acid generator contained as an optional component in the resist underlayer film-forming composition of the present invention can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonic acid salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0079] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0080] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0081] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0082] Examples of disulfonyldiazomethane 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 acid generators may be used singly or in combination of two or more.

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

[0085] <Crosslinking agent> Examples of crosslinking agents that may be included as an optional component in the resist underlayer film-forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK (registered trademark) 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0086] The crosslinking agent of the present application may also be a nitrogen-containing compound having, per molecule, 2 to 6 substituents bonded to nitrogen atoms and represented by the following formula (1d), as described in WO 2017 / 187969:

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

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

[0089] [ka]

[0090] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents bonded to a nitrogen atom in one molecule represented by the following formula (2d) with at least one compound represented by the following formula (3d):

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

[0092] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril 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 represent an alkyl group having 1 to 4 carbon atoms.) Examples of glycoluril derivatives represented by the formula (2E) include compounds represented by the following formulae (2E-1) to (2E-4): Furthermore, examples of compounds represented by the formula (3d) include compounds represented by the following formulae (3d-1) and (3d-2):

[0094] [ka] [ka]

[0095] The entire disclosure of WO2017 / 187969 is incorporated herein by reference with respect to the content of the nitrogen-containing compound having, per molecule, 2 to 6 substituents bonded to the nitrogen atom and represented by the following formula (1d):

[0096] The crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2), which is described in WO 2014 / 208542.

[0097] [ka] (In the formula, Q 1 represents a single bond or a monovalent organic group, and R 1 and R 4 each represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R 2 and R 5 each represents a hydrogen atom or a methyl group, and R 3 and R 6 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n1 is an integer satisfying 1≦n1≦3, n2 is an integer satisfying 2≦n2≦5, n3 is an integer satisfying 0≦n3≦3, n4 is an integer satisfying 0≦n4≦3, and 3≦(n1+n2+n3+n4)≦6. n5 is an integer in the range of 1≦n5≦3, n6 is an integer in the range of 1≦n6≦4, n7 is an integer in the range of 0≦n7≦3, n8 is an integer in the range of 0≦n8≦3, and 2≦(n5+n6+n7+n8)≦5. 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 reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0099] [ka] (In the formula, Q 2 represents a single bond or a divalent organic group. 8 , R 9 , R 11 and R 12 each represents a hydrogen atom or a methyl group, and R 7 and R 10 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n9 is an integer in the range of 1≦n9≦3, n10 is an integer in the range of 2≦n10≦5, n11 is an integer in the range of 0≦n11≦3, n12 is an integer in the range of 0≦n12≦3, and 3≦(n9+n10+n11+n12)≦6. n13 is an integer satisfying 1≦n13≦3, n14 is an integer satisfying 1≦n14≦4, n15 is an integer satisfying 0≦n15≦3, n16 is an integer satisfying 0≦n16≦3, and 2≦(n13+n14+n15+n16)≦5. m2 represents an integer from 2 to 10.

[0100] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] Examples of the compounds represented by formula (G-3) and formula (G-4) include the following.

[0107] [ka]

[0108] [ka] In the formula, Me represents a methyl group.

[0109] The entire disclosure of WO 2014 / 208542 is incorporated herein by reference.

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

[0111] <Other ingredients> The resist underlayer film-forming composition of the present invention may further contain a surfactant in order to prevent pinholes, striations, etc., and further improve coating properties against surface irregularities. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate; polyoxyethylene sorbitan monopalmitate; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-containing surfactants such as F-TOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

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

[0113] <Resist Underlayer Film> The resist underlayer film according to the present invention can be produced by applying the above-described resist underlayer film-forming composition onto a semiconductor substrate and baking it.

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

[0115] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin-coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

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

[0117] The thickness of the resist underlayer film to be formed may be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5 nm) to 0.05 μm (5 nm) μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), 0.005 μm (5 nm). 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 be decomposed by heat.

[0118] <Method for manufacturing a patterned substrate, and method for manufacturing a semiconductor device> The manufacturing method of a patterned substrate involves the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist formed on the resist underlayer film by coating and baking using a method known per se 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 of suitable photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Chemical Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[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, WO2019 / 123842 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

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

[0121] An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by general formula (21):

[0122] [ka] In the general formula (21), m represents an integer of 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 which may have a substituent or a single bond.

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

[0127] M + 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 Periods 3 to 7 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) containing 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 having 6 to 20 carbon atoms. 1 is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R 1 are the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 3 is a monovalent group having 1 to 20 carbon atoms and containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0131] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit having an acid labile group; and an acid generator.

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

[0133] Examples of the resist film include the following.

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

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

[0136] Examples of resist materials include the following:

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

[0138] [ka] (In formula (b1) and formula (b2), R A is a hydrogen atom or a methyl group. 1 is a single bond or an ester group. 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a part 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 substituted with a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 may combine to form a carbonyl group. 1 ~R 5 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amido group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and in which some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate ester group. 1 and R 2 may be bonded to form a ring together with the sulfur atom to which they are attached.

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

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

[0141] [ka] [In formula (f2-r-1), Rf 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0142] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0143] [ka] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have a substituent. 01 R is a single bond or a divalent linking group. 2 are each independently an organic group having a fluorine atom.

[0144] Coatings, coating solutions, and coating compositions include, for example:

[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 / hydroxyl-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, a 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), a coating solution comprising a 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, a coating solution.

[0149] An inorganic pattern-forming precursor aqueous solution comprising water, a metal oxide cation, a polyatomic inorganic anion, and a mixture with a radiation-sensitive ligand containing a peroxide group.

[0150] The exposure is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used, but the resist underlayer film-forming composition of the present 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 is appropriately selected from 10 seconds to 300 seconds. Examples of alkaline developers include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, aqueous solutions of the above alkalis can be used with the addition of an appropriate amount of alcohols such as isopropyl alcohol or a nonionic surfactant. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of using an alkaline developer, development can be performed with an organic solvent such as butyl acetate to develop portions of the photoresist where the alkaline dissolution rate is not improved. Through the above steps, a substrate having the resist patterned thereon can be produced.

[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, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the substrate is processed by a method known per se (e.g., dry etching), thereby manufacturing a semiconductor device. [Example]

[0152] The present invention will now be described in detail 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 were measured by gel permeation chromatography (hereinafter abbreviated as GPC). The measurements were performed using a GPC device manufactured by Tosoh Corporation under the following conditions:

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

[0155] <Synthesis Example A1> In a reaction vessel, 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 dissolved in 35.85 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A1 (compound A1) had a weight-average molecular weight of 860 and a polydispersity of 1.1, calculated in terms of standard polystyrene. The structure present in polymer A1 (compound A1) is shown below. [ka]

[0156] <Synthesis example A2> In a reaction vessel, 8.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 added and dissolved in 56.85 g of propylene glycol monomethyl ether. After replacing the atmosphere in 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 showed that the resulting polymer A2 (compound A2) had a weight-average molecular weight of 1,140 and a polydispersity of 1.0, calculated in terms of standard polystyrene. The structure present in polymer A2 (compound A2) is shown in the following formula. [ka]

[0157] <Synthesis example A3> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 4.76 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 0.55 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 45.68 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A3. GPC analysis showed that the resulting polymer A3 had a weight-average molecular weight of 5,400 and a polydispersity of 3.4, calculated in terms of standard polystyrene. The structure present in polymer A3 is shown in the following formula. [ka]

[0158] <Synthesis example A4> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 2.99 g of trans-p-coumaric acid (Tokyo Chemical Industry Co., Ltd.), 1.24 g of 4-nitrocinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.55 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 43.60 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A4. GPC analysis showed that the resulting polymer A4 had a weight-average molecular weight of 2,800 and a polydispersity of 3.0, calculated as standard polystyrene. The structure present in polymer A4 is shown below. [ka]

[0159] <Synthesis example A5> In a reaction vessel, 8.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 5.13 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 1.66 g of 4-nitrocinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.73 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.16 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 62.70 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing Polymer A5. GPC analysis showed that the resulting Polymer A5 had a weight-average molecular weight of 2,900 and a polydispersity of 2.4, calculated as standard polystyrene. The structure present in Polymer A5 is shown below. [ka]

[0160] <Synthesis example A6> In a reaction vessel, 10.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 5.75 g of α-cyano-4-hydroxycinnamic acid (Midori Chemical Industry Co., Ltd.), 2.07 g of 4-nitrocinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.91 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.20 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 28.39 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing Polymer A6. GPC analysis showed that the resulting Polymer A6 had a weight-average molecular weight of 2,700 and a polydispersity of 2.3, calculated as standard polystyrene. The structure present in Polymer A6 is shown below. [ka]

[0161] <Synthesis example A7> A reaction vessel was charged with 9.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 5.77 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 1.45 g of terephthalaldehyde acid (Tokyo Chemical Industry Co., Ltd.), and 0.82 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 39.76 g of propylene glycol monomethyl ether were dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours. Subsequently, a solution of 0.64 g of malononitrile (Junsei Chemical Co., Ltd.) dissolved in 1.50 g of propylene glycol monomethyl ether was added to the system, and the reaction was continued for an additional 4 hours to obtain a solution containing polymer A7. GPC analysis showed that the resulting polymer A7 had a weight-average molecular weight of 3,900 and a polydispersity of 2.5, calculated as standard polystyrene. The structure present in polymer A7 is shown below.

[0162] [ka]

[0163] <Synthesis example A8> In a reaction vessel, 6.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 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 added and dissolved in 62.98 g of propylene glycol monomethyl ether. After replacing the atmosphere in 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 showed that the resulting polymer A8 had a weight-average molecular weight of 5,400 and a polydispersity of 3.1, calculated in terms of standard polystyrene. The structure present in polymer A8 is shown in the following formula.

[0164] [ka]

[0165] <Synthesis example A9> In a reaction vessel, 4.00 g of resorcinol diglycidyl ether (product name: EX-201, manufactured by Nagase ChemteX Corporation), 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 and dissolved in 46.27 g of propylene glycol monomethyl ether. After replacing the atmosphere in 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 showed that the resulting polymer A9 had a weight-average molecular weight of 6,200 and a polydispersity of 4.3, calculated in terms of standard polystyrene. The structure present in polymer A9 is shown in the following formula.

[0166] [ka]

[0167] <Synthesis Example A10> In a reaction vessel, 9.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.20 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 5.06 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), and 0.58 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 40.00 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A10 had a weight-average molecular weight of 3,900 and a polydispersity of 2.8, calculated as standard polystyrene. The structure present in polymer A10 is shown below.

[0168] [ka]

[0169] <Synthesis Example A11> In a reaction vessel, 15.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 4.21 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 26.48 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A11. GPC analysis showed that the resulting polymer A11 had a weight-average molecular weight of 3,200 and a polydispersity of 2.3, calculated in terms of standard polystyrene. The structure present in polymer A11 is shown in the following formula.

[0170] [ka]

[0171] <Synthesis Example A12> In a reaction vessel, 15.00 g of a 30 wt% solution of monomethyldiglycidyl isocyanuric acid in PGME (manufactured by Shikoku Chemical Industry Co., Ltd.), 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 and dissolved in 28.87 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A12. GPC analysis showed that the resulting polymer A12 had a weight-average molecular weight of 1,600 and a polydispersity of 2.3, calculated in terms of standard polystyrene. The structure present in polymer A12 is shown in the following formula.

[0172] [ka]

[0173] <Synthesis Example A13> In a reaction vessel, 15.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.40 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 1.03 g of adamantanecarboxylic acid (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 3.73 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A13. GPC analysis showed that the resulting polymer A13 had a weight-average molecular weight of 3,500 and a polydispersity of 3.3, calculated as standard polystyrene. The structure present in polymer A13 is shown below.

[0174] [ka]

[0175] <Synthesis Example A14> In a reaction vessel, 15.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.40 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 2.22 g of 3,5-diiodosalicylic acid (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 5.52 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A13 had a weight-average molecular weight of 2,000 and a polydispersity of 2.0, calculated as standard polystyrene. The structure present in polymer A13 is shown below.

[0176] [ka]

[0177] <Synthesis Example A15> In a reaction vessel, 15.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.40 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 1.10 g of 4-nitrocinnamic acid (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 27.67 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A15. GPC analysis showed that the resulting polymer A15 had a weight-average molecular weight of 3,100 and a polydispersity of 2.4, calculated as standard polystyrene. The structure present in polymer A15 is shown below.

[0178] [ka]

[0179] <Synthesis example A16> In a reaction vessel, 15.00 g of a 30 wt% N,N-diglycidyl-5,5-dimethylhydantoin PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.40 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 2.64 g of tetrabromophthalic anhydride (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 6.15 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A16 had a weight-average molecular weight of 2,300 and a polydispersity of 1.9, calculated in terms of standard polystyrene. The structure present in polymer A16 is shown below.

[0180] [ka]

[0181] <Synthesis Example A17> In a reaction vessel, 15.00 g of a 30 wt% solution of monomethyldiglycidyl isocyanuric acid in PGME (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.21 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.97 g of adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 25.94 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A17 had a weight-average molecular weight of 1,300 and a polydispersity of 2.3, calculated in terms of standard polystyrene. The structure present in polymer A17 is shown below.

[0182] [ka]

[0183] <Synthesis Example A18> In a reaction vessel, 12.00 g of a 30 wt% monomethyldiglycidyl isocyanuric acid PGME solution (Shikoku Chemical Industry Co., Ltd.), 2.41 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 2.23 g of 3,5-diiodosalicylic acid (Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 25.97 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer A18 had a weight-average molecular weight of 1,600 and a polydispersity of 2.2, calculated as standard polystyrene. The structure present in polymer A18 is shown below.

[0184] [ka]

[0185] <Synthesis Example A19> In a reaction vessel, 15.00 g of a 30 wt% monomethyldiglycidyl isocyanuric acid PGME solution (Shikoku Chemical Industry Co., Ltd.), 3.21 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 2.49 g of tetrabromophthalic anhydride (Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 32.02 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer A19. GPC analysis showed that the resulting polymer A19 had a weight-average molecular weight of 2,000 and a polydispersity of 2.1, calculated as standard polystyrene. The structure present in polymer A19 is shown below.

[0186] [ka]

[0187] <Comparative Synthesis Example A1> In a reaction vessel, 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added and dissolved in 682.00 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing Comparative Polymer A1. GPC analysis showed that the obtained Comparative Polymer A1 had a weight average molecular weight of 6,800 and a polydispersity of 4.8, calculated as standard polystyrene. The structure present in Comparative Polymer A1 is shown in the following formula. [ka]

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

[0189] <Comparative synthesis example A3> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 4.10 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 43.06 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing Comparative Polymer A3. GPC analysis showed that the obtained Comparative Polymer A3 had a weight-average molecular weight of 7,400 and a polydispersity of 4.8, calculated in terms of standard polystyrene. The structure present in Comparative Polymer A3 is shown below. [ka]

[0190] <Comparative synthesis example A4> In a reaction vessel, 5.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 3.68 g of 5-methoxyisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.10 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 36.94 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing Comparative Polymer A4. GPC analysis showed that the resulting Comparative Polymer A4 had a weight-average molecular weight of 7,300 and a polydispersity of 5.2, calculated as standard polystyrene. The structure present in Comparative Polymer A4 is shown below. [ka]

[0191] (Preparation of resist underlayer film) (Examples and Comparative Examples) The polymers (compounds), crosslinking agents, curing catalysts (acid generators), and solvents obtained in 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 mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare solutions of compositions for forming resist underlayer films.

[0192] In Tables A1 and A2, tetramethoxymethyl glycoluril 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]- is abbreviated as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid is abbreviated as PyPSA, surfactant is abbreviated as R-30N, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. The amounts of each additive are shown in parts by mass.

[0193] [Table 1]

[0194] [Table 2]

[0195] (Photoresist solvent elution test) Each of the resist underlayer film-forming compositions of Examples A1 to A19 and Comparative Examples A1 to A4 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 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 a solvent used in photoresists. A change in film thickness of less than 5 Å was rated as good, and a change in film thickness of 5 Å or more was rated as bad. The results are shown in Table A3.

[0196] [Table 3]

[0197] (Resist patterning evaluation) [Resist pattern formation test using an electron beam lithography device] The resist underlayer film-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 film with a thickness of 5 nm. A positive EUV resist solution was spin-coated onto the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography system (ELS-G130). After exposure, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (Tokyo Ohka Kogyo Co., Ltd., product 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 (Hitachi High-Technologies Corporation, CG4100) was used to measure the resist pattern. The photoresist patterns thus obtained were evaluated for the possibility of forming 22 nm lines and spaces (L / S). Formation of a 22 nm L / S pattern was confirmed in all cases of Examples A1 to A19. Formation of a 22 nm L / S pattern was not confirmed in Comparative Example A3. The amount of charge required to form a 22 nm line / 44 nm pitch (line and space (L / S=1 / 1)) was defined as the optimal irradiation energy, and the irradiation energy (μC / cm 2 The minimum CD size and LWR at which no collapse was observed within the resist pattern shot are shown in Table A4. Improvements in LWR and minimum CD size were confirmed in Examples A1 to A19 compared to Comparative Examples A1 to A4.

[0198] [Table 4]

[0199] <Synthesis Example B1> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 2.99 g of trans-p-coumaric acid (Tokyo Chemical Industry Co., Ltd.), 0.95 g of trans-cinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.55 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 42.44 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B1. GPC analysis showed that the resulting polymer B1 had a weight-average molecular weight of 2,900 and a polydispersity of 2.3, calculated as standard polystyrene. The structure present in polymer B1 is shown in the following formula. [ka]

[0200] <Synthesis example B2> In a reaction vessel, 6.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 2.99 g of trans-p-coumaric acid (Tokyo Chemical Industry Co., Ltd.), 1.04 g of 4-methylcinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.55 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.12 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 42.44 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer B2. GPC analysis showed that the resulting polymer B2 had a weight-average molecular weight of 3,000 and a polydispersity of 2.2, calculated as standard polystyrene. The structure present in polymer B2 is shown below. [ka]

[0201] <Synthesis Example B3> In a reaction vessel, 35.00 g of a propylene glycol monomethyl ether solution of 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene (DIC Corporation, product name WR-400), 1.99 g of 5,5-diethylbarbituric acid (Tateyama Chemical Co., Ltd.), 0.57 g of trans-cinnamic acid (Tokyo Chemical Industry Co., Ltd.), and 0.32 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added and dissolved in 5.10 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing Polymer B3. GPC analysis showed that the resulting Polymer B3 had a weight-average molecular weight of 3,700 and a polydispersity of 2.1, calculated as standard polystyrene. The structure present in Polymer B3 is shown below. [ka]

[0202] <Synthesis example B4> In a reaction vessel, 6.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 dissolved in 36.48 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer B4 (compound B4) had a weight-average molecular weight of 680 and a polydispersity of 1.1, calculated in terms of standard polystyrene. The structure present in polymer B4 (compound B4) is shown below. [ka]

[0203] <Synthesis Example B5> In a reaction vessel, 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 dissolved in 32.26 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer B5 (compound B5) had a weight-average molecular weight of 760 and a polydispersity of 1.1, calculated in terms of standard polystyrene. The structure present in polymer B5 (compound B5) is shown below. [ka]

[0204] <Synthesis example B6> In a reaction vessel, 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 dissolved in 34.23 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer B6 (compound B6) had a weight-average molecular weight of 760 and a polydispersity of 1.0, calculated in terms of standard polystyrene. The structure present in polymer B6 (compound B6) is shown below. [ka]

[0205] <Synthesis Example B7> In a reaction vessel, 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 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 dissolved in 32.72 g of propylene glycol monomethyl ether. 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 showed that the resulting polymer B7 (compound B7) had a weight-average molecular weight of 810 and a polydispersity of 1.0, calculated in terms of standard polystyrene. The structure present in polymer B7 (compound B7) is shown below. [ka]

[0206] <Comparative Synthesis Example B1> In a reaction vessel, 100.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid (Tateyama Chemicals Corporation), and 4.1 g of benzyltriethylammonium chloride were added and dissolved in 682.00 g of propylene glycol monomethyl ether. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing comparative polymer B1. GPC analysis showed that the obtained comparative polymer B1 had a weight average molecular weight of 6,800 and a polydispersity of 4.8, calculated as standard polystyrene. The structure present in comparative polymer B1 is shown in the following formula. [ka]

[0207] <Comparative synthesis example B2> In a reaction vessel, 40.00 g of a propylene glycol monomethyl ether solution of 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene (manufactured by DIC Corporation, trade name: WR-400), 2.87 g of trans-p-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.37 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.08 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 5.95 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing Comparative Polymer B2. GPC analysis showed that the resulting Comparative Polymer B2 had a weight-average molecular weight of 6,200 and a polydispersity of 3.0, calculated in terms of standard polystyrene. The structure present in Comparative Polymer B2 is shown below. [ka]

[0208] (Preparation of resist underlayer film) (Examples and Comparative Examples) The polymers (compounds) obtained in Synthesis Examples B1 to B7 and Comparative Synthesis Examples B1 and B2, crosslinking agents, curing catalysts, and solvents were mixed in the proportions shown in Tables B1 and B2, and the mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare solutions of compositions for forming resist underlayer films. In Tables B1 and B2, tetramethoxymethyl glycoluril 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]- is abbreviated as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid is abbreviated as PyPSA, surfactant is abbreviated as R-30N, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. The amounts of each additive are shown in parts by mass.

[0209] [Table 5]

[0210] [Table 6]

[0211] (Photoresist solvent elution test) Each of the resist underlayer film-forming compositions of Examples B1 to B7 and Comparative Examples B1 and B2 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 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 a solvent used in photoresists. A change in film thickness of less than 5 Å was rated as good, and a change in film thickness of 5 Å or more was rated as bad. The results are shown in Table B3.

[0212] [Table 7]

[0213] (Resist patterning evaluation) [Resist pattern formation test using an electron beam lithography device] The resist underlayer film-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 film with a thickness of 5 nm. A positive EUV resist solution was spin-coated onto the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography system (ELS-G130). After exposure, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (Tokyo Ohka Kogyo Co., Ltd., product 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 (Hitachi High-Technologies Corporation, CG4100) was used to measure the resist pattern. The photoresist patterns thus obtained were evaluated for the possibility of forming 22 nm lines and spaces (L / S). In all cases of Examples B1 to B7, the formation of 22 nm L / S patterns was confirmed. The amount of charge required to form 22 nm lines / 44 nm pitch (line and space (L / S=1 / 1)) was defined as the optimum irradiation energy, and the irradiation energy (μC / cm 2 ) and LWR are shown in Table B4. In Examples B1 to B7, improvements in LWR were confirmed compared to Comparative Examples B1 and B2.

[0214] [Table 8]

[0215] <Synthesis example C1> A reaction vessel was charged with 9.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 5.77 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 1.45 g of terephthalaldehyde acid (Tokyo Chemical Industry Co., Ltd.), and 0.82 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 39.76 g of propylene glycol monomethyl ether were dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours. Subsequently, a solution of 0.64 g of malononitrile (Junsei Chemical Co., Ltd.) dissolved in 1.50 g of propylene glycol monomethyl ether was added to the system, and the reaction was continued for an additional 4 hours to obtain a solution containing polymer C1. GPC analysis showed that the resulting polymer C1 had a weight-average molecular weight of 3,900 and a polydispersity of 2.5, calculated as standard polystyrene. The structure present in polymer C1 is shown in the following formula. [ka]

[0216] <Synthesis Example C2> In a reaction vessel, 5.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 3.21 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 0.79 g of 3-cyanobenzoic acid (Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were dissolved in 37.81 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer C2. GPC analysis showed that the resulting polymer C2 had a weight-average molecular weight of 3,300 and a polydispersity of 2.4, calculated as standard polystyrene. The structure present in polymer C2 is shown below. [ka]

[0217] <Synthesis Example C3> In a reaction vessel, 5.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemical Industry Co., Ltd.), 3.21 g of 5-nitroisophthalic acid (Tokyo Chemical Industry Co., Ltd.), 0.93 g of α-cyanocinnamic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.10 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were dissolved in 38.76 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer C3. GPC analysis showed that the resulting polymer C3 had a weight-average molecular weight of 2,900 and a polydispersity of 2.3, calculated as standard polystyrene. The structure present in polymer C3 is shown below. [ka]

[0218] <Comparative Synthesis Example C1> In a reaction vessel, 100.00 g of monoallyl diglycidyl isocyanurate (Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid (Tateyama Chemicals Corporation), and 4.1 g of benzyltriethylammonium chloride were dissolved in 682.00 g of propylene glycol monomethyl ether. After replacing the atmosphere in 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 showed that the obtained comparative polymer C1 had a weight average molecular weight of 6,800 and a polydispersity of 4.8, calculated as standard polystyrene. The structure present in comparative polymer C1 is shown in 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 Industries, Ltd.), 9.67 g of terephthalaldehyde acid (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. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 135°C for 6 hours. Next, 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 continued for another 2 hours to obtain a solution containing comparative polymer C2 (comparative compound C2). GPC analysis showed that the obtained comparative polymer C2 (comparative compound C2) had a weight average molecular weight of 980 and a dispersity of 1.3, calculated in terms of standard polystyrene. The structure present in comparative polymer C2 (comparative compound C2) is shown in the following formula. [ka] (L1 represents the bond with L2 and L3)

[0220] (Preparation of resist underlayer film) (Examples and Comparative Examples) The polymers (compounds) obtained in Synthesis Examples C1 to C3 and Comparative Synthesis Examples C1 to C2, crosslinking agents, curing catalysts, and solvents were mixed in the proportions shown in Tables C1 and C2, and the mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare solutions of compositions for forming resist underlayer films. In Tables C1 and C2, tetramethoxymethyl glycoluril 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]- is abbreviated as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid is abbreviated as PyPSA, surfactant is abbreviated as R-30N, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. The amounts of each additive are shown in parts by mass.

[0221] [Table 9]

[0222] [Table 10]

[0223] (Photoresist solvent elution test) Each of the resist underlayer film-forming compositions of Examples C1 to C3 and Comparative Examples C1 and C2 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 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 a solvent used in photoresists. A change in film thickness of less than 1 Å was rated as good, and a change in film thickness of 1 Å or more was rated as bad. The results are shown in Table C3.

[0224] [Table 11]

[0225] (Resist patterning evaluation) [Resist pattern formation test using an electron beam lithography device] The resist underlayer film-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 film with a thickness of 5 nm. A positive EUV resist solution was spin-coated onto the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography system (ELS-G130). After exposure, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (Tokyo Ohka Kogyo Co., Ltd., product 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 (Hitachi High-Technologies Corporation, CG4100) was used to measure the resist pattern. The photoresist patterns thus obtained were evaluated for the possibility of forming 22 nm lines and spaces (L / S). In all cases of Examples C1 to C3, the formation of 22 nm L / S patterns was confirmed. The amount of charge required to form 22 nm lines / 44 nm pitch (line and space (L / S=1 / 1)) was defined as the optimum irradiation energy, and the irradiation energy (μC / cm 2 The minimum CD size and LWR at which no collapse was observed within the resist pattern shot are shown in Table C4. Improvements in LWR and minimum CD size were confirmed in Examples C1 to C3 compared to Comparative Example C1.

[0226] [Table 12] [Industrial Applicability]

[0227] The resist underlayer film-forming composition according to the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, as well as a method for producing a substrate having a resist pattern and a method for producing a semiconductor device using the resist underlayer film-forming composition.

Claims

1. A resist underlayer film-forming composition comprising a polymer and a solvent, The following formula (103): 【Chemistry 1】 In formula (103), Ar represents an aromatic ring having 6 to 40 carbon atoms which may be substituted, and L １ represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms, and n represents an integer of 1 to 3, at a terminal of the polymer.

2. 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 reactive with the epoxy groups.

3. 3. The resist underlayer film forming composition according to claim 2, wherein the compounds (A) and (B) contain a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

4. 3. The resist underlayer film forming composition according to claim 2, wherein the compound (A) containing two epoxy groups is selected from the group consisting of the following formulas: 【Chemistry 2】 【Transformation 3】

5. 4. The resist underlayer film forming composition according to claim 1, wherein the aromatic ring having 6 to 40 carbon atoms is selected 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.

6. 4. The resist underlayer film-forming composition according to claim 3, wherein the heterocycle is selected from 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, triazinone, triazinedione, and triazinetrione.

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

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

9. A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of claims 1 to 8.

10. A step of applying the resist underlayer film-forming composition according to any one of claims 1 to 8 onto a semiconductor substrate and baking the composition to form a resist underlayer film; a step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

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

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