Composition of the resist underlayer film, resist underlayer film and manufacturing method of semiconductor device

Abstract

This invention provides a novel composition for a formation inhibitor underlayer film, which addresses the requirement for a high-hardness film that can self-cure at low temperatures even without acid catalysts and crosslinking agents, reducing sublimation content and exhibiting high flexural strength. It can also be used as a crosslinking agent, demonstrating higher planarization and heat resistance than conventional crosslinking agents, while maintaining the same embedding properties. Optical constants and etching resistance can be freely varied by selecting the monomers. The composition of the formation inhibitor underlayer film of this invention comprises a polymer (X) and a solvent. The polymer (X) is a repeating structural unit containing an aromatic compound A having a ROCH2- group (R being a monovalent organic group, hydrogen atom, or a mixture thereof) and an aromatic compound B having 120 or fewer carbon atoms different from A, linked by a -O- cross-bonding, and consisting of 1 to 6 repeating structural units for each A bonded to 1 B.

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film of a sintered coating film formed from the composition, and a method for manufacturing a semiconductor device using the composition. [Previous Technology]

[0002] In the manufacture of semiconductor devices, fine processing using photolithography is performed. In this photolithography process, when an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser exposes a resist layer on a substrate, it is known that the standing wave generated by the reflection of the ultraviolet laser on the substrate surface can prevent the formation of a resist pattern with the desired shape. To solve this problem, a resist underlayer film (anti-reflective film) is disposed between the substrate and the resist layer. Therefore, phenolic varnish resin is known to be used as a component for forming the resist underlayer film.

[0003] Furthermore, in order to achieve the thinning of the resist layer required for miniaturizing the resist pattern, it is also known to form at least two resist underlayer films and use these resist underlayer films as masking materials in photolithography processes. Examples of materials for forming the aforementioned at least two layers include organic resins (e.g., acrylic resins, phenolic varnish resins), silicone resins (e.g., organic polysiloxanes), and inorganic silicone compounds (e.g., SiON, SiO2). When using a pattern formed from the aforementioned organic resin layer as a mask for dry etching, the pattern must be etch-resistant to etching gases (e.g., fluorocarbons).

[0004] As a composition for forming such resistive underlayer films, for example, Patent Document 1 discloses a composition comprising a polymer having a structural unit represented by the following formula (1) and a solvent for forming a resistive underlayer film:

[0005]

[0006] (In the formula, X1 represents a divalent organic group having at least one aromatic ring with 6 to 20 carbon atoms that can be substituted by a halogen group, nitro group, amino group, or hydroxyl group, or an organic group having at least one aromatic ring with 6 to 20 carbon atoms that can be substituted by a halogen group, nitro group, amino group, or hydroxyl group, or a methoxy group). [Prior Art Documents] [Patent Documents]

[0007] [Patent Document 1] WO2014 / 171326A1 [Summary of the Invention]

[0008] [The problem the invention aims to solve]

[0009] However, conventional compositions of the resist underlayer film, if lacking acid catalysts or crosslinking agents, cannot self-harden at low temperatures, resulting in sublimation that contaminates the device. This makes it unsatisfactory in terms of achieving a high-hardness film with high flexural resistance. Therefore, there is a need to improve upon these aspects by ensuring the film does not dissolve in the resist solvent, maintains the desired optical constants and etching resistance, and addresses the aforementioned issues. [Means for solving the problem]

[0010] The present invention is intended to solve the above-mentioned problems. That is, the present invention includes the following. [1] A composition for forming a resisting underlayer film, comprising a polymer (X) and a solvent, wherein the polymer (X) contains an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom or a mixture thereof) and an aromatic compound B having 120 or less carbon atoms different from A, which are linked by a repeating structural unit of a linker-O- cross-bonding, and is a repeating structural unit of 1 to 6 Bs bonded to 1 A. [2] The composition for forming a resisting underlayer film as in [1], wherein the polymer (X) contains a repeating structural unit represented by formula (1), (in formula (1), A1 represents an organic group derived from an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom or a mixture thereof), and B1 represents an organic group derived from an aromatic compound B having 120 or less carbon atoms different from A1). [3] As in [2], the composition of the lower layer of the inhibitor is formed, wherein the R in formula (1) can be substituted with phenyl, naphthyl or anthracene, and can be a saturated or unsaturated straight or branched C2-C20 aliphatic or C3-C20 alicyclic hydrocarbon group, hydrogen atom or a mixture thereof interrupted by oxygen atom, nitrogen atom or carbonyl group. [4] As in [2], the composition of the lower layer film forming the inhibitor, wherein B1 in formula (1) is represented by the following formula (2), (in formula (2), C1 and C2 each independently represent an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms or a hydrocarbon group containing an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms, Y represents a single bond, carbonyl, sulfonyl, -CR12- or -(CF3)C(CF3)-, R1 represents a carbonyl group that may be interrupted by an oxygen atom, carbonyl, nitrogen atom, carbon-carbon double bond or carbon-carbon triple bond, and the carbon-carbon double bond or carbon-carbon triple bond may be bonded to a terminal alkyl group with 1 to 10 carbon atoms, hydroxyl group, hydrogen atom, halogen, aromatic hydrocarbon group with 6 to 20 carbon atoms or -NR22, R2 represents a carbon-carbon double bond or carbon-carbon triple bond that can be interrupted, and the carbon-carbon double bond or carbon-carbon triple bond can be bonded to a chain or cyclic alkyl group with 1 to 10 carbon atoms at the end, i is 0 or 1, and the dashed line represents the bond with an oxygen atom). [5] The composition of the lower layer film of the forming inhibitor as in [4], wherein i in formula (2) is 1. [6] The composition of the lower layer film of the forming inhibitor as in [4] or [5], wherein the polymer (X) further contains a repeating structural unit represented by formula (3), (in formula (3), B1 is represented by the aforementioned formula (2), and A2 represents an organic group derived from an aromatic compound A' with 120 or fewer carbon atoms, which is different from B1). [7] The composition of the lower layer film of the forming inhibitor as in any of [2] to [6], wherein A1 in formula (1) does not have a phenolic hydroxyl group. [8] The composition of the forming inhibitor underlayer film of any of [1] to [6], wherein the polymer (X) has an aromatic hydrocarbon group with 6 to 30 substituted carbon atoms at at least one end.[9] A composition of a forming inhibitor underlayer film as described in any one of [1] to [8], further comprising a membrane material (Z) capable of crosslinking with polymer (X).

[10] A composition of a forming inhibitor underlayer film as described in any one of [1] to [9], further comprising a crosslinking agent.

[11] A composition of a forming inhibitor underlayer film as described in any one of [1] to

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

[12] A composition of a forming inhibitor underlayer film as described in any one of [1] to

[11] , further comprising a surfactant.

[13] A composition of a forming inhibitor underlayer film as described in any one of [1] to

[12] , wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

[14] An inhibitor underlayer film, characterized in that it is a sintered product of a coated film formed from a composition as described in any one of [1] to

[13] .

[15] A method for manufacturing a semiconductor device includes the following steps: forming a resist underlayer film on a semiconductor substrate using any one of the components of [1] to

[13] ; forming a resist film on the formed resist underlayer film; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing it; etching the aforementioned resist underlayer film through the formed resist pattern and patterning it; and processing a semiconductor substrate through the patterned resist underlayer film.

[16] A method for manufacturing a semiconductor device includes the following steps: forming a resist underlayer film on a semiconductor substrate using a composition of any one of [1] to

[13] ; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing; etching the hard mask through the formed resist pattern and patterning it; etching the resist underlayer film through the patterned hard mask and patterning it; and processing the semiconductor substrate through the patterned resist underlayer film.

[17] In the method for manufacturing a semiconductor device as described in

[15] or

[16] , the step of forming the resist underlayer film is performed by nanoimprint lithography. [Effects of the Invention].

[0011] According to the present invention, a novel composition for forming an inhibitory underlayer film can be provided, which should be able to obtain a high-hardness film that can self-cured at low temperatures even without acid catalysts and crosslinking agents, can reduce the amount of sublimation and has high flexural strength, and can also be used as a crosslinking agent, showing higher planarization and higher heat resistance than conventional crosslinking agents, and the embedding properties are the same as conventional products, and the optical constants and etching resistance can be freely changed by selecting monomers.

Implementation Method

[0013] The composition of the lower layer film forming inhibitor of the present invention comprises a polymer (X) and a solvent. The polymer (X) is a repeating structural unit containing an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) and an aromatic compound B having 120 or fewer carbon atoms different from A, which are linked by a linker group -O- cross-bonding, and is a repeating structural unit that bonds 1 to 6 Bs to 1 A.

[0014] [Polymer(X)] Polymer(X) is a repeating structural unit containing an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) and an aromatic compound B having 120 or fewer carbon atoms different from A, which are linked by a linker group -O- cross-bonding, and is a repeating structural unit with 1 to 6, more preferably 1 to 4, more preferably 2 to 4, even more preferably 2 to 3, and most preferably 2 B bonds to 1 A bond.

[0015] The preferred polymer (X) contains repeating structural units represented by formula (1). (In formula (1), A1 represents an organic group derived from an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and B1 represents an organic group derived from an aromatic compound B having 120 or fewer carbon atoms, which is different from A1).

[0016] The preferred polymer (X) further contains repeating structural units represented by formula (3). (In formula (3), B1 is represented by the aforementioned formula (2), and A2 represents an organic group derived from an aromatic compound A' with 120 or fewer carbon atoms, which is different from B1).

[0017] The R of the monovalent organic group is preferably substituted with phenyl, naphthyl, or anthracene, and can be a saturated or unsaturated straight-chain or branched C2-C20 aliphatic or C3-C20 alicyclic hydrocarbon group, a hydrogen atom, or a mixture thereof, interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group. The term "mixture" means that the plurality of ROCH2- groups present in a single building unit can be different, and also means that the ROCH2- groups in each of two or more building units can be different.

[0018] Typical saturated aliphatic hydrocarbon groups are alkyl groups having a straight chain or branches and having 2 to 20 carbon atoms. Examples include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3- Methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, and 1-methoxy-2-propyl, etc.

[0019] Cyclic alkyl groups may also be used, for example, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclopropyl Butyl, 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-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0020] Typically, the aforementioned unsaturated aliphatic hydrocarbon groups are alkenyl groups with 2 to 20 carbon atoms. Examples include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl- 3-Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl 2-n-Propyl-2-propenyl, 3-Methyl-1-pentenyl, 3-Methyl-2-pentenyl, 3-Methyl-3-pentenyl, 3-Methyl-4-pentenyl, 3-Ethyl-3-butenyl, 4-Methyl-1-pentenyl, 4-Methyl-2-pentenyl, 4-Methyl-3-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1-Methyl-2-ethyl-2-propenyl, 1-Dibutylvinyl, 1,3-Dimethyl-1- Butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tertiary butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentene The list includes 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, etc.

[0021] Preferred R is -H, -CH3 group, -CH2CH3 group, -CH2CH2CH3 group, -CH2CH2CH2CH3 group, cyclohexyl group and -CH(CH3)CH2OCH3 group.

[0022] B1 in formula (1) is preferred as expressed in the following formula (2). (In formula (2), C1 and C2 each independently represent an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms or a hydrocarbon group containing an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms; Y represents a single bond, carbonyl, sulfonyl, -CR12- group or -(CF3)C(CF3)- group; R1 represents a group that can be interrupted by an oxygen atom, carbonyl, nitrogen atom, carbon-carbon double bond or carbon-carbon triple bond, and the carbon-carbon double bond or carbon-carbon triple bond can be bonded to a terminal alkyl group with 1 to 10 carbon atoms, hydroxyl, hydrogen atom, halogen, aromatic hydrocarbon group with 6 to 20 carbon atoms or -NR22; R2 represents a group that can be interrupted by a carbon-carbon double bond or carbon-carbon triple bond, and the carbon-carbon double bond or carbon-carbon triple bond can be bonded to a terminal chain or cyclic alkyl group with 1 to 10 carbon atoms; i is 0 or 1; the dashed line represents the bond with an oxygen atom).

[0023] Preferably, C1 and C2 each have electron-withdrawing substituents independent of the aromatic ring. There are no particular limitations on the electron-withdrawing substituents, but examples include cyano, ketone, nitro, aldehyde, carboxyl, ester, etc. In preferred formula (2), i is 1.

[0024] The polymer (X) can be synthesized by polymerizing an aromatic compound A having a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), an aromatic compound B having 120 or fewer carbon atoms different from A, and a compound containing a functional group that serves as a linker (e.g., aldehyde, ketone, ROCH2-Ar-CH2OR (R is a monovalent organic group, a hydrogen atom, or a mixture thereof)), and further an aromatic compound A' having 120 or fewer carbon atoms different from B1, in the presence of an alkaline catalyst (e.g., sodium hydroxide, potassium hydroxide, potassium carbonate, trimethylamine, triethylamine, etc.).

[0025] The aromatic compound A used in the synthesis of polymer (X) having a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) is preferably an aromatic compound with 120 or fewer carbon atoms. Aromatic compound A, provided it contains a ROCH2- group, can be: (a) a monocyclic compound such as benzene; (b) a condensed ring compound such as naphthalene, anthracene, or pyrene; (c) a heterocyclic compound such as furan, pyrrole, thiophene, pyridine, carbazole, iminostilbene, phenothiazine, indole, or indolecarbazole; (d) a compound in which the aromatic rings of (a) to (c) of biphenyl, phenylindole, α,α,α',α'-tetra(4-hydroxyphenyl)-p-xylene, or calixarenes are linked by single or extended alkyl bonds; and (e) a compound such as 2,2-diphenylpropane with -(CH2)n- (n=1~20), -CH=CH-, -C≡C-, -N=N-, -NH-, -NR-, or -NHCO-. Compounds in which aromatic rings (a) to (d) are linked by spacer groups exemplified by -NRCO-, -S-, -COO-, -O-, -CO-, and -CH=N-; (f) compounds containing 9,9-bis(4-hydroxyphenyl) benzox, benzox as described below, or compounds having a benzox skeleton. The examples above are not limited to these.

[0026] Examples of aromatic compound A are not limited to these, but include, provided that it has a ROCH2- group, benzene, biphenyl, 2,2-diphenylpropane, thiophene, furan, pyridine, pyrimidine, pyrazine, pyrrole, oxazole, thiazole, imidazole, naphthalene, anthracene, quinoline, carbazole, quinazoline, purine, indoleazine, benzothiophene, benzofuran, indole, phenylindole, acridine, and fumonisin. More specifically, 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, etc. Examples of aromatic compound A further include fumonisin or compounds having a fumonisin skeleton as shown below.

[0027] The aromatic compound A, which is the starting material of polymer (X), may have phenolic hydroxyl groups, but A1 in preferred formula (1) does not have phenolic hydroxyl groups. The term "does not have phenolic hydroxyl groups" means that when measured by analytical means such as NMR, the amount of phenolic hydroxyl groups is below the detection limit, or even if detected, it is at most a trace amount.

[0028] Aromatic compound B is an aromatic compound with 120 or fewer carbon atoms, which is different from aromatic compound A. The description of aromatic compound B is the same as that for aromatic compound A. Aromatic compound B preferably has a halogen on its aromatic ring, more preferably has two or more halogens, and fluorine is preferred as the halogen. Examples of aromatic compound B are not limited to these, but include 2,5-difluorotoluene, 2,5-difluoroaniline, 2,5-difluorophenol, 1,2,3-trifluorobenzene, 2,5-difluorobenzonitrile, 2,5-difluorobenzaldehyde, 2,5-difluorobenzylamine, 2,5-difluorobenzyl alcohol, 2,5-difluoroanisole, 2,3,6-trifluorophenol, 2,5-difluorophenylacetonitrile, 4-amino-2,5-difluorobenzonitrile, 2,5-difluorophenyl isocyanate, 2,5-difluoroacetophenone, 2,3,5-trifluorobenzonitrile, 2,4,5-trifluorobenzonitrile, 2,5-difluorobenzoic acid, 2,5-difluoronitrobenzene, and 2,4,5-trifluorobenzyl alcohol. 2,5-Difluorobenzyl chloride, 2,3,5,6-tetrafluorophenol, 1,2-difluorobenzene, 2,3-difluorotoluene, 3,4-difluorotoluene, 3,4-difluoroaniline, 2,3-difluoroaniline, 2,3-difluorophenol, 3,4-difluorophenol, 4-ethynyl-1,2-difluorobenzene, 3,4-difluorobenzonitrile, 2,3-difluorobenzonitrile, 2,3-difluorobenzaldehyde, 3,4-difluorobenzaldehyde, 2,3-difluorobenzylamine, 3,4-difluorobenzyl alcohol, 3,4-difluoroanisole, 2,3-difluoroanisole, 2,3-difluorobenzyl alcohol, 3,4-difluorothiol, 2,3,4-trifluorophenol, 2,3,6-trifluorophenol, 2, 3-Difluoroacetonitrile, 3,4-difluorophenyl isocyanate, 5-ethynyl-1,2,3-trifluorobenzene, 3,4-difluoroacetophenone, 2,3,4-trifluorobenzonitrile, 3,4,5-trifluorobenzonitrile, 2,3-difluorobenzoic acid, 3,4-difluorobenzoic acid, 3,4-difluoronitrobenzene, 4,5-difluorodinitro, 2,3,4-trifluorobenzaldehyde, 3,4,5-trifluorobenzaldehyde, 2,3,6-trifluorobenzaldehyde, 1,3-difluorobenzene, 2,4-difluorotoluene, 2,6-difluorotoluene, 3,5-difluoroaniline, 2,6-difluoroaniline, 3,5-difluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 1,3, 5-Trifluorobenzaldehyde, 1-ethynyl-2,4-difluorobenzene, 1-ethynyl-3,5-difluorobenzene, 2,6-difluorobenzonitrile, 3,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 3,5-difluorobenzaldehyde, 2,6-difluorobenzaldehyde, 2,4-difluorobenzaldehyde, 1-ethyl-3,5-difluorobenzaldehyde, 3,5-difluorobenzonitrile, 2,6-difluorobenzylaniline, 2,4-difluorobenzyl alcohol, 2,4-difluoroanisole, 3,5-difluorobenzyl alcohol, 3,5-difluoroanisole, 2,6-difluorobenzyl alcohol, 2,6-difluoroanisole, 2,4-difluorothiol, 2,6-difluorophenylacetonitrile, 3,5-difluorophenylacetonitrile, 2,4-Difluorophenylacetonitrile, 2,4-difluorophenyl isocyanate, 2,6-difluoro-4-hydroxybenzonitrile, 1,3-difluoro-5-propylbenzene, 2,4,6-trifluorobenzonitrile, 2,6-difluorobenzoic acid, 2,4-difluorobenzoic acid, 3,5-difluorobenzoic acid, 2,6-difluoronitrobenzene, 3,5-difluoronitrobenzene, 2,4,6-trifluorobenzaldehyde, 2,4,5-trifluorobenzyl alcohol, 2,6-difluorobenzyl chloride, 2,6-difluoronaphthalene, 3,6-difluoronaphthalene, 1,5-difluoronaphthalene, 2,7-Difluoronaphthalene, 1,6-Difluoronaphthalene, 1,2-Difluoronaphthalene, 1,7-Difluoronaphthalene, 1,3-Difluoronaphthalene, 1,4-Difluoronaphthalene, 2,2-Difluorobiphenyl, 4,4-Difluorobiphenyl, 9,9-bis(fluorophenyl)furan, bis(fluoronaphthyl)furan, 9,9-bis(4-fluorophenyl)furan, 1,4-Difluorobenzene, 4,4'-Difluorodiphenylmethane, 4,4-Difluorobenzophenone, preferably 1,4-difluorobenzene, 4,4'-difluorodiphenylmethane, and 4,4-difluorobenzophenone.

[0029] Aromatic compound A' is an aromatic compound with 120 or fewer carbon atoms, which is determined by the derivation of an organogroup different from B1. The description of aromatic compounds is the same as that for aromatic compound A. Examples of aromatic compounds A' are not limited to these, but include hydroquinone, resorcinol, catechol, pyrogallol, 2,6-dihydroxynaphthalene, 3,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4-biphenol, 4,4',4''-trihydroxytriphenylmethane, calixarenes, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, and bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, dihydroxycarbazole, dihydroxyphenylamine, α,α,α',α'-tetra(4-hydroxyphenyl)-p-xylene, 9,9-bis(hydroxyphenyl)furan, bis(hydroxynaphthyl)furan, 1,5-dihydroxynaphthalene, 2,2-bisphenol, 1,1,1-tris(4-hydroxyphenyl)ethane, etc., preferably 9,9-bis(4-hydroxyphenyl)furan, 1,5-dihydroxynaphthalene, 2,2-biphenol, 1,1,1-tris(4-hydroxyphenyl)ethane.

[0030] The compounds used in the synthesis of polymer (X) are not limited to one compound, and two or more compounds may be used together. Therefore, the repeating structural units of aromatic compound A with a ROCH2- group and aromatic compound B with 120 or fewer carbon atoms that are different from A via the linker group -O- cross-bonding may be the same or different.

[0031] The polymer (X) may have an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted at at least one end. Examples of such aromatic hydrocarbon groups include phenyl or naphthyl groups that can be substituted with vinyl groups.

[0032] In this invention, the characteristic is that the aromatic compound A, aromatic compound B, and any selected aromatic compound A' are formed by repeating structural units with linker-O- cross-bonding.

[0033] The weight average molecular weight of the polymer (X) contained in the composition of the lower layer film forming the inhibitor of the present invention is not particularly limited. It is converted to a standard polystyrene value, for example, 500 or more, for example, 1,000 or more, for example, 2,000 or more, for example, 500,000 or less, for example, 100,000 or less.

[0034] [Solvent] The composition of the lower layer film forming inhibitor of the present invention can be prepared by dissolving the above components in a suitable solvent and used in a homogeneous solution state.

[0035] Examples of solvents that can be used include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl cellolytic acetate, ethyl cellolytic acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0036] In addition, high-boiling-point solvents with a boiling point of 180°C or higher may also be used. Specific examples of high-boiling-point organic solvents include 1-octadecanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, and acetic acid. Nonyl ester, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol n-butyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ... diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Diethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetate, propylene glycol... Diacetyl alcohol, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc.

[0037] These solvents may be used alone or in combination of two or more. The proportion of solids removed from the aforementioned composition by the organic solvent is, for example, 0.5% by mass to 30% by mass, preferably 0.8% by mass to 15% by mass.

[0038] Also, the following compounds described in WO2018 / 131562A1 may be used. (R1, R2 and R3 in formula (i) each represent an alkyl group with 1 to 20 carbon atoms that can be interrupted by hydrogen, oxygen, sulfur or amide bonds. They may be the same or different from each other, or they may be bonded together to form a ring structure).

[0039] As an alkyl group having 1 to 20 carbon atoms, examples include straight-chain or branched alkyl groups that may have substituents or not, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, cyclohexyl, 2-ethylhexyl, n-nonyl, isononyl, p-tert-butylcyclohexyl, n-decyl, n-dodecylnonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. Preferably, it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0040] An alkyl group having 1 to 20 carbon atoms interrupted by an oxygen atom, sulfur atom, or amide bond, for example containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. -O-, -S-, -NHCO-, or -CONH- may be one or more units in the aforementioned alkyl group. Specific examples of alkyl groups with 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, etc., and further include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl, each of which may be substituted with methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, etc. Methoxy, ethoxy, methylthio, and ethylthio are preferred, and methoxy and ethoxy are even more preferred.

[0041] Because these solvents have relatively high boiling points, they are also effective in imparting high embedding and high planarization properties to the composition forming the lower layer film of the inhibitor.

[0042] The following shows specific examples of preferred compounds represented by formula (i).

[0043] Among the above, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamine and compounds represented by the following formula are preferred, with 3-methoxy-N,N-dimethylpropionic acid and N,N-dimethylisobutylamine being particularly preferred compounds represented by formula (i).

[0044] These solvents can be used alone or in combination of two or more. Preferably, these solvents have a boiling point of 160°C or higher, and are preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamine, 2,5-dimethylhexane-1,6-dimethyldiacetate (DAH; CAS, 89182-68-3), and 1,6-diethoxyhexane (CAS, 6222-17-9). Particularly preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutylamine.

[0045] [Any component] The composition of the lower layer film of the forming inhibitor of the present invention may further contain at least one of the following as an arbitrary component: a crosslinking agent, an acid and / or an acid generating agent, a thermal acid generating agent and a surfactant.

[0046] (Crosslinking Agent) The composition of the lower layer film of the formation inhibitor of the present invention may further contain a crosslinking agent. As the aforementioned crosslinking agent, a crosslinking compound having at least two crosslinking-forming substituents is preferred. Examples include melamine-based compounds, substituted urea-based compounds, and phenolic compounds or polymer systems of the like having crosslinking-forming substituents such as hydroxymethyl or methoxymethyl. Specifically, compounds such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, etc., such as tetramethoxymethylglycourea, tetrabutoxymethylglycourea, and hexamethoxymethylmelamine. Furthermore, as substituted urea-based compounds, compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea, such as tetramethoxymethyl urea and tetrabutoxymethyl urea, are used. Condensations of these compounds may also be used. Examples of phenolic compounds include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol, tetrahydroxymethylbisphenol, tetramethoxymethylbisphenol, and compounds represented by the following formula.

[0047] Compounds having at least two epoxy groups may also be used as the aforementioned crosslinking agent. Examples of such compounds include, for instance, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexane dicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid ester, trimethylolethane triglycidyl ether, and bisphenol A-diglycidyl ether. Ethers, DAICEL (stock)'s EPOLIDE [registered trademark] GT-401, same as GT-403, same as GT-301, same as GT-302, CELLOXIDE [registered trademark] 2021, same as 3000, Mitsubishi Chemical (stock)'s 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872, Nippon Kayaku (stock)'s EPPN201, same as 202, EOCN-102, same as 103S, same as 104S, same as 1020, same as 1025, same as 1027, NAGASE CHEMTEX (stock) manufactures DENACOL [registered trademark] EX-252, EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321; BASF (stock) manufactures CY175, CY177, CY179, CY182, CY184, CY192; DIC (stock) manufactures EPICLON 200, 400, 7015, 835LV, and 850CRP. As compounds having at least two epoxy groups, epoxy resins having amine groups may also be used. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.).

[0048] As the aforementioned crosslinking agent, compounds having at least two end-capped isocyanate groups may also be used. Examples of such compounds include, for instance, TAKENATE B-830 and B-870N manufactured by Mitsui Chemicals, Inc., and VESTANAT B1358 / 100 manufactured by EVONIK DEGUSSA Co., Ltd.

[0049] As the aforementioned crosslinking agent, a compound having at least two vinyl ether groups may also be used. Examples of such compounds include, for instance, bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, divinyl adipate, diethylene glycol divinyl ether, 1,2,4-tris(4-vinyloxybutyl)phenyltricarboxylate, 1,3,5-tris(4-vinyloxybutyl)phenyltricarboxylate, bis(4-(vinyloxy)butyl)terephthalate, bis(4-(vinyloxy)butyl)isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, and cyclohexanediol divinyl ether.

[0050] Furthermore, as the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. Preferably, a compound containing a crosslinking substituent with an aromatic ring (e.g., benzene ring, naphthalene ring) within its molecule is used as the crosslinking agent with high heat resistance.

[0051] Examples of such compounds include compounds having a partial structure of formula (4) below, and polymers or oligomers having repeating units of formula (5) below. R11, R12, R13 and R14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and such alkyl groups may be those exemplified above.

[0052] The compounds, polymers and oligomers of formulas (4) and (5) are exemplified below.

[0053] The above-mentioned compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, in the above-mentioned crosslinking agents, the compound of formula (4-23) was obtained from Honshu Chemical Co., Ltd. under the trade name TMOM-BP, and the compound of formula (4-24) was obtained from Asahi Organic Materials Co., Ltd. under the trade name TM-BIP-A. The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but can be 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more relative to the total solids, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less. Although such crosslinking agents may sometimes cause crosslinking reactions due to self-condensation, when crosslinking substituents are present in the above-mentioned polymers of the present invention, crosslinking reactions with such crosslinking substituents can occur.

[0054] One of the various crosslinking agents can be added, or two or more can be added in combination.

[0055] (Acid and / or its salt and / or acid generating agent) The composition of the lower layer film of the forming inhibitor of the present invention may include acid and / or its salt and / or acid generating agent.

[0056] Examples of acids include carboxylic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphtholic acid, or inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Salts of the above-mentioned acids may also be used as salts. The use of salts is not limited, but salts of ammonia derivatives such as trimethylamine salts and triethylamine salts, or salts of pyridine derivatives and morpholine derivatives, are preferred. Only one acid and / or its salt may be used, or two or more may be used in combination. The amount of the mixture relative to the total solids is typically 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0057] Examples of acid generating agents include thermal acid generating agents and photosensitive acid generating agents. Examples of thermal acid generating agents include 2,4,4,6-tetrabromocyclohexanedione, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by KING Industrial Co., Ltd.), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of other agents include quaternary ammonium salts of trifluoroacetic acid and organic sulfonic acid alkyl esters.

[0058] The photoacid generating agent generates acid during resist exposure. Therefore, the acidity of the lower film can be adjusted. This is a method for matching the acidity of the lower film with the acidity of the upper resist. Furthermore, by adjusting the acidity of the lower film, the shape of the resist pattern formed on the upper layer can be adjusted. Examples of photoacid generating agents contained in the composition of the resist-forming lower film of the present invention include onium salt compounds, sulfonylimine compounds, and disulfonyldiazomethane compounds.

[0059] Examples of onium salt compounds include diphenylmonium hexafluorophosphate, diphenylmonium trifluoromethane sulfonate, diphenylmonium nonafluoron-butane sulfonate, diphenylmonium perfluoron-octane sulfonate, diphenylmonium camphor sulfonate, bis(4-tert-butylphenyl)monium camphor sulfonate and bis(4-tert-butylphenyl)monium trifluoromethane sulfonate, and strontium salt compounds such as triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butane sulfonate, triphenylstrontium camphor sulfonate and triphenylstrontium trifluoromethane sulfonate.

[0060] Examples of sulfonamide compounds include, for example, N-(trifluoromethanesulfonoxy)succinimide, N-(nonafluoron-butanesulfonoxy)succinimide, N-(camphorsulfonoxy)succinimide and N-(trifluoromethanesulfonoxy)naphthylimide.

[0061] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane, etc.

[0062] The acid generating agent may be used alone or in combination with two or more. When using the acid generating agent, its proportion relative to 100 parts by weight of the solid fraction of the composition forming the lower layer film of the inhibitor is 0.01 to 10 parts by weight, or 0.1 to 8 parts by weight, or 0.5 to 5 parts by weight.

[0063] (Surfactant) The composition of the photoresist underlayer film of the present invention may further contain a surfactant. Examples of the aforementioned surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. (EFTOP [registered trademark]) Fluorinated surfactants such as EF301, EF303, EF352 (Mitsubishi Materials Electronics & Chemicals Co., Ltd.), MEGAFAC [registered trademark] F171, F173, R-30, R-30-N, R-40, R-40-LM (DIC Co., Ltd.), FLUORAD FC430, FC431 (Sumitomo 3M Co., Ltd.), ASAHIGUARD [registered trademark] AG710, SURFLON [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.). One type of surfactant can be added, or a combination of two or more can be added. The aforementioned surfactant content, relative to the solid content after removing the solvent from the composition of the underlying film of the forming agent of the present invention, is, for example, 0.01% by mass to 5% by mass.

[0064] [Membrane Material (Z)] The polymer (X) of the present invention can also be used as a crosslinking agent for the membrane material (Z). That is, the composition of the lower membrane of the forming inhibitor of the present invention further includes a membrane material (Z) that can undergo a crosslinking reaction with the polymer (X). The membrane material (Z) can be described as a membrane material that can undergo a crosslinking reaction with the polymer (X).

[0065] Any membrane material (Z) selected for use in this invention may be used without particular restriction, as long as it is a material capable of undergoing a crosslinking reaction with the aforementioned polymer (X). The membrane material may be a polymer, an oligomer, or a low-molecular-weight compound with a molecular weight of 1,000 or less. Examples of crosslinking-forming groups present in the membrane material include hydroxyl, carboxyl, amino, and alkoxy groups, but are not limited to these.

[0066] More specifically, the membrane materials disclosed in section [Membrane Materials (Y)] of specification WO2021 / 172295 (Japanese Patent Application 2020-033333) can be cited as examples.

[0067] The crosslinkable membrane material (Z) described above preferably includes at least one selected from the group consisting of: (Y1) membrane materials containing aliphatic rings (e.g., (a) above), (Y2) aldehyde varnish membrane materials (e.g., (b), (c), (d), (e), (f), (g), (h), (i), (j), (k), (l) above), (Y3) polyether membrane materials (e.g., (z) above), (Y4) polyester membrane materials (e.g., (o), (p) above), (Y5) compounds different from the crosslinking compound (A) (e.g., (n), (r), (s), (t), (u), (v), (w), (x), (y) above), (Y6) membrane materials containing aromatic condensation rings (e.g., (q) above), (Y7) acrylic resin, and (Y8) methacrylic resin.

[0068] When the composition of the lower layer membrane of the forming inhibitor of the present invention contains a crosslinkable membrane material (Z) (membrane material or polymer), the content ratio of the aforementioned crosslinkable membrane material (Z) relative to the total solids is generally 1 to 99.9% by mass, preferably 50 to 99.9% by mass, more preferably 50 to 95% by mass, and even more preferably 50 to 90% by mass.

[0069] The composition of the resist underlayer film of the present invention may further include light absorbers, rheology modifiers, adhesion promoters, etc. Rheology modifiers can effectively improve the flowability of the composition forming the underlayer film. Adhesion promoters can effectively improve the adhesion between the semiconductor substrate or the resist and the underlayer film.

[0070] (Light Absorber) Commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC Publishing) or "Dye Handbook" (Organic Synthetic Chemistry Society) are preferred as light absorbers, such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31 CI Dispersible Red 1, 44, 57, 72 and 73; CI Dispersible Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Dispersible Violet 43; CI Dispersible Blue 96; CI Fluorescent Brightener 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The above-mentioned absorbers are generally formulated in a ratio of 10% by mass or less, preferably 5% by mass or less, relative to the total solids content of the components forming the lower layer film of the resist.

[0071] (Rheology Modifier) ​​The main purpose of adding a rheology modifier is to improve the flowability of the composition forming the lower layer film of the resist, especially during the baking process, to improve the uniformity of the film thickness of the lower layer film of the resist and to improve the filling ability of the composition forming the lower layer film of the resist to the pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecanyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically formulated at a ratio of less than 30% by mass relative to the total solids of the composition forming the lower layer of the resist film.

[0072] (Adhesion Additives) The main purpose of adding adhesion additives is to improve the adhesion between the substrate or resist and the components forming the resist underlayer film, especially to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldioxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; and hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium. The additives include silanes such as hydroxymethyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adsorption aids are typically formulated at a ratio of less than 5% by mass, preferably less than 2% by mass, relative to the total solids content of the composition forming the lower layer film of the resistor.

[0073] The solid content of the composition of the forming inhibitor lower layer film of the present invention is generally 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content refers to the proportion of all components after the solvent is removed from the composition of the forming inhibitor lower layer film. The proportions of the above polymers in the solid content are preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0074] One of the criteria for evaluating whether the composition of the resisting lower membrane is a homogeneous solution is to observe the permeability of a specific microfilter. However, the composition of the resisting lower membrane of the present invention can pass through a microfilter with a pore size of 0.1 μm and presents a homogeneous solution.

[0075] Examples of materials for the microfilters include fluorinated resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polyurethane), PES (polyether ether), and nylon, but PTFE (polytetrafluoroethylene) is preferred.

[0076] [Resistor Underlayer Film] The resistor underlayer film can be formed using the composition of the present invention for forming the resistor underlayer film as follows. The composition of the present invention for forming the resistor underlayer film is applied to a substrate used in the manufacture of semiconductor devices (e.g., silicon wafer substrate, silicon dioxide coated substrate (SiO2 substrate), silicon nitride substrate (SiN substrate), silicon oxynitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), tungsten substrate (W substrate), glass substrate, ITO substrate, polyimide substrate, and low dielectric constant material (low-k material) coated substrate, etc.) using a suitable coating method such as a spin coater or coater. Subsequently, the resistor underlayer film is formed by firing using a heating means such as a heating plate. The firing conditions can be appropriately selected from a firing temperature of 80°C to 600°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is between 150°C and 350°C, and the firing time is between 0.5 and 2 minutes. The ambient gas used during firing can be air, or an inert gas such as nitrogen or argon. Here, the thickness of the underlying film formed is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz imprinting mold (mold replica) can be fabricated.

[0077] Furthermore, an adhesion layer and / or a polysiloxane layer containing 99% by mass or less or 50% by mass of Si can also be coated or deposited on the resist lower layer film of the present invention. For example, in addition to forming the adhesion layer described in Japanese Patent Application Publication No. 2013-202982 or Japanese Patent No. 5827180, or the silicon-containing resist lower layer film (inorganic resist lower layer film) described in WO2009 / 104552A1, a Si-based inorganic material film can also be formed by CVD or the like.

[0078] Furthermore, the composition of the forming resist lower layer film of the present invention can reduce the step difference between the part with step difference and the part without step difference by coating it onto a semiconductor substrate (so-called step difference substrate) with a step difference and a part without step difference and firing it.

[0079] [Method for Manufacturing a Semiconductor Device] The method for manufacturing a semiconductor device of the present invention includes the following steps: forming a resistive underlayer film using the composition of the present invention for forming a resistive underlayer film; forming a resistive film on the formed resistive underlayer film; forming a resistive pattern by irradiating the formed resistive film with light or electron lines and developing it; etching the aforementioned resistive underlayer film through the formed resistive pattern and patterning it; and processing a semiconductor substrate through the patterned resistive underlayer film.

[0080] Furthermore, the method for manufacturing a semiconductor device according to the present invention includes the following steps: forming a resist lower layer film using the composition of the present invention; forming a hard mask on the formed resist lower layer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing it; etching the aforementioned hard mask and patterning the formed resist pattern through the hard mask; etching the aforementioned resist lower layer film and patterning the patterned hard mask through the patterned hard mask; and processing a semiconductor substrate through the patterned resist lower layer film.

[0081] The steps for forming a resistive underlayer film using the composition of the present invention are as described above.

[0082] Alternatively, an organopolysiloxane film can be formed on the resist lower layer film formed by the aforementioned steps as a second resist lower layer film, and a resist pattern can be formed on it. The second resist lower layer film can be a SiON film or a SiN film formed by vapor deposition methods such as CVD or PVD. Furthermore, an antireflective film (BARC) can be formed on the second resist lower layer film as a third resist lower layer film, and the third resist lower layer film can also be a resist shape correction film without antireflective properties.

[0083] In the aforementioned step of forming the resist pattern, exposure is performed by using a mask (reticle) to form the specific pattern or by direct drawing. Exposure sources can include, for example, g-lines, i-lines, KrF excimer lasers, ArF excimer lasers, EUV, and electron beams. After exposure, post-exposure heating (post-exposure baking) is performed as needed. Subsequently, development is performed with a developer (e.g., a 2.38% by mass tetramethylammonium hydroxide aqueous solution), followed by rinsing with a rinsing solution or pure water to remove the developer used. Then, the resist pattern is dried and baked to improve adhesion to the substrate.

[0084] The etching step performed after the formation of the resist pattern is carried out by dry etching. Examples of etching gases used in dry etching include CHF3, CF4, and C2F6 for the second resist underlayer film (organopolysiloxane film), O2, N2O, and NO2 for the first resist underlayer film formed from the composition of the present invention, and CHF3, CF4, and C2F6 for surfaces with steps, recesses, and / or protrusions. Furthermore, argon, nitrogen, or carbon dioxide can also be mixed into these gases.

[0085] [Formation of a resist underlayer film using nanoimprinting] The above-described steps for forming a resist underlayer film can also be performed using nanoimprinting. This method includes the steps of applying a curable composition to the formed resist underlayer film, contacting the curable composition with a mold, irradiating the curable composition with light or electron beams to form a curable film, and separating the curable film from the mold.

[0086] The polymer (X) of the present invention is expected to exhibit good permeability to gases such as He, H2, N2, and air, as well as good embedding properties, hardness, and flexural strength. By modifying the molecular skeleton, the optical constants and etching rates can be adjusted to suit the process. Details are disclosed, for example, in the section on [Formation of Resistor Underlayer Film Using Nanoimprinting] of WO2021 / 172295 (Japanese Patent Application 2020-033333). [Examples]

[0087] Hereinafter, specific examples of the composition of the present invention will be described using the following embodiments, but the present invention will not be limited thereto.

[0088] The apparatus used to determine the weight-average molecular weight of the reaction products obtained in the following synthetic examples is shown. Apparatus: HLC-8320GPC manufactured by TOSOH Corporation; GPC column: TSKgel Super-Multipore HZ-N (2 columns); Column temperature: 40°C; Flow rate: 0.35 ml / min; Dissolution solution: THF; Standard sample: Polystyrene.

[0089] The chemical structure (example) and abbreviation of the main raw materials used are as follows.

[0090]

[0091] [Synthesis Example 1] 12.00 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 7.23 g of 4,4-difluorobenzophenone (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as DFBP), 4.78 g of potassium carbonate (manufactured by Fuji Film and Koimitsu Pure Chemical Industries Co., Ltd.), and 56.01 g of N-methylpyrrolidone (hereinafter referred to as NMP) were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 4.5 hours. After the reaction was stopped, the potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water = 90 / 10 (vol / vol) solution to reprecipitate, and then filtered by suction. The resulting precipitate was dried to obtain resin (1-1). The weight-average molecular weight (Mw) determined by GPC to be converted to polystyrene was approximately 7,300. The obtained resin was dissolved in propylene glycol monomethyl ether (hereinafter referred to as PGMEA), and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0092]

[0093] [Synthesis Example 2] 15.00 g of TMOM-BP, 4.52 g of DFBP, 4.23 g of 4,4'-difluorodiphenylmethane, 2.99 g of potassium carbonate, and 52.51 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen atmosphere and reacted for approximately 4.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed, followed by suction filtration. The resulting precipitate was dried to obtain resin (1-2). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 5,100. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0094]

[0095] [Synthesis Example 3] 12.00 g of TMOM-BP, 11.60 g of 9,9-bis(4-hydroxyphenyl)furan (Tokyo Chemical Industry Co., Ltd.), 14.45 g of DFBP, 9.55 g of potassium carbonate, and 111.06 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 3.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. 1N-HCl was added to the resulting filtrate to neutralize it, and the mixture was stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed, followed by suction filtration. The resulting precipitate was dried to obtain resin (1-3). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 6,500. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0096]

[0097] [Synthesis Example 4] 15.00 g of TMOM-BP, 6.63 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 18.06 g of DFBP, 11.93 g of potassium carbonate, and 120.45 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 1.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed by suction filtration. The resulting precipitate was dried to obtain resin (1-4). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 7,600. The obtained resin was dissolved in propylene glycol monomethyl ether (hereinafter referred to as PGME), and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0098]

[0099] [Synthesis Example 5] 15.00 g of TMOM-BP, 2.36 g of 1,4-difluorobenzene (Tokyo Kasei Corporation, hereinafter referred to as DFB), 4.52 g of DFBP, 5.97 g of potassium carbonate, and 25.49 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 3 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water = 90 / 10 (vol / vol) solution, and the precipitate was collected and filtered by suction. The resulting precipitate was dried to obtain resin (1-5). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 15,200. The obtained resin was dissolved in cyclohexanone (hereinafter referred to as CYH), and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0100]

[0101] [Synthesis Example 6] 10.00 g of TMOM-BP, 1.10 g of 1-naphthol, 7.53 g of DFBP, 4.97 g of potassium carbonate, and 55.07 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 4.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed by suction filtration. The resulting precipitate was dried to obtain resin (1-6). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 5,700. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0102]

[0103] [Synthesis Example 7] 12.00 g of TMOM-BP, 0.81 g of 4-fluorostyrene (Tokyo Chemical Co., Ltd.), 5.78 g of DFBP, 4.77 g of potassium carbonate, and 54.51 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 4.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed, followed by suction filtration. The resulting precipitate was dried to obtain resin (1-8). The weight-average molecular weight (Mw) determined by GPC to be converted to polystyrene was approximately 14,400. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0104]

[0105] [Synthesis Example 8] 12.00 g of TMOM-BP, 2.64 g of 2,2-biphenol (Tokyo Kasei Corporation), 5.78 g of DFBP, 10.32 g of potassium carbonate, and 78.93 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 4 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed by suction filtration. The resulting precipitate was dried to obtain resin (1-9). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 5,000. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0106]

[0107] [Synthesis Example 9] 12.00 g of TMOM-BP, 4.30 g of 1,1,1-tris(4-hydroxyphenyl)ethane (Tokyo Chemical Co., Ltd.), 10.32 g of DFBP, 8.86 g of potassium carbonate, and 82.80 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 1.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed by suction filtration. The resulting precipitate was dried to obtain resin (1-10). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 7,500. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0108]

[0109] [Synthesis Example 10] 8.00 g of TMOM-BP, 1.92 g of TM-BIP-A, 6.02 g of DFBP, 3.98 g of potassium carbonate, and 46.48 g of NMP were placed in a flask. The mixture was then heated to 100°C under nitrogen atmosphere and reacted for approximately 5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 70 / 30 (vol / vol), and precipitation was performed, followed by suction filtration. The resulting precipitate was dried to obtain resin (1-11). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 4,400. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0110]

[0111] [Synthesis Example 11] 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.63 g of 9-fentanyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.30 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.93 g of PGMEA were placed in a 100 mL flask. The mixture was then heated to reflux under nitrogen for approximately 1.5 hours. The precipitate was then precipitated with methanol and dried to obtain polymer (1-12). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 2,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and an anion exchange resin for 4 hours to obtain the desired polymer solution.

[0112]

[0113] [Comparative Synthesis Example 1] 5.00 g of 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl, 4.50 g of DFBP, 2.97 g of potassium carbonate, and 29.11 g of NMP were placed in a flask. The mixture was then heated to 150°C under nitrogen and reacted for approximately 4.5 hours. After the reaction was stopped, potassium carbonate was removed by filtration. The resulting filtrate was neutralized by adding 1N-HCl and stirred for a period of time. This diluted solution was added dropwise to a methanol / water solution of 90 / 10 (vol / vol), and precipitation was performed by suction filtration. The resulting precipitate was dried to obtain resin (2-1). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 1,500. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound.

[0114]

[0115] [Example 1] A resin solution (17.17% by mass) was obtained in Synthesis Example 1. 0.17g of TMOM-BP (Honshu Chemical Co., Ltd.), 1.95g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass surfactant (DIC Co., Ltd., MEGAFAC R-40), 5.57g of PGMEA, and 2.93g of PGME were added to 4.97g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0116] [Example 2] A resin solution (17.17% by mass) was obtained in Synthesis Example 1. 1.53g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.10g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 4.75g of PGMEA, and 2.69g of PGME were added to 5.93g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0117] [Example 3] A resin solution (17.17% by mass) was obtained in Synthesis Example 1. 0.24g of PGMEA, 0.52g of PGMEA, and 5.28g of PGME, each containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), were added to 13.96g of this resin solution and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution that forms the composition of the lower layer membrane of the inhibitor.

[0118] [Example 4] A resin solution (solids 14.96% by mass) was obtained in Synthesis Example 2. 0.17g of TMOM-BP, 1.28g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 4.83g of PGMEA, and 2.93g of PGME were added to 5.70g of this resin solution and dissolved. The solution was then filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0119] [Example 5] A resin solution (solids 17.90% by mass) was obtained in Synthesis Example 3. 0.17g of TMOM-BP, 1.28g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 5.77g of PGMEA, and 2.91g of PGME were added to 4.77g of this resin solution and dissolved. The solution was then filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0120] [Example 6] A resin solution (17.39% by mass) was obtained in Synthesis Example 4. 0.17g of TMOM-BP, 1.28g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 4.10g of PGMEA, and 4.46g of PGME were added to 4.90g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0121] [Example 7] A resin solution (solids 17.40% by mass) was obtained in Synthesis Example 5. 0.17g of TMOM-BP, 1.28g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 4.10g of PGMEA, 1.54g of PGME, and 2.93g of CYH were added to 4.90g of the resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0122] [Example 8] A resin solution (21.61% by mass) was obtained in Synthesis Example 6. 0.16g of TMOM-BP, 1.22g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.08g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 3.27g of PGMEA, and 1.51g of PGME were added to 3.76g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0123] [Example 9] A resin solution (19.85% by mass) was obtained in Synthesis Example 7. 0.16g of TMOM-BP, 1.22g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.08g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 2.94g of PGMEA, and 1.51g of PGME were added to 4.09g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0124] [Example 10] A resin solution (20.06% by mass) was obtained in Synthesis Example 8. 0.16g of TMOM-BP, 1.22g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.08g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 2.98g of PGMEA, and 1.51g of PGME were added to 4.05g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0125] [Example 11] A resin solution (19.38% by mass) was obtained in Synthesis Example 9. 0.16g of TMOM-BP, 1.22g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.08g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 2.84g of PGMEA, and 1.51g of PGME were added to 4.19g of this resin solution and dissolved. The solution was filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0126] [Example 12] A resin solution (17.52% by mass) was obtained in Synthesis Example 10. 0.17g of TMOM-BP, 1.28g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.09g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 5.66g of PGMEA, and 2.91g of PGME were added to 4.87g of this resin solution and dissolved. The solution was then filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer of the inhibitor film.

[0127] [Example 13] A resin solution (30.00% by mass) was obtained in Synthesis Example 11. 1.51g of the resin solution (17.17% by mass) obtained in Synthesis Example 1, 1.95g of PGME containing 2% by mass pyridinium p-hydroxybenzenesulfonate, 0.13g of PGMEA containing 1% by mass surfactant (DIC Corporation, MEGAFAC R-40), 10.31g of PGMEA, and 1.77g of PGME were added to 4.33g of the resin solution and dissolved. The solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the composition forming the lower layer membrane of the inhibitor.

[0128] [Comparative Example 1] A resin solution (solids 18.37% by mass) was obtained in Comparative Synthesis Example 1. 0.19g of TMOM-BP, 1.46g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.10g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 5.21g of PGMEA, and 2.71g of PGME were added to 5.31g of this resin solution and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the composition forming the lower layer membrane of the inhibitor.

[0129] [Comparative Example 2] A resin solution (30.00% by mass) was obtained in Synthesis Example 11. 0.26g of TMOM-BP, 1.95g of PGME containing 2% by mass of pyridinium p-hydroxybenzenesulfonate, 0.13g of PGMEA containing 1% by mass of surfactant (DIC Corporation, MEGAFAC R-40), 11.56g of PGMEA, and 1.77g of PGME were added to 4.33g of this resin solution and dissolved. The solution was then filtered through a 0.1μm PTFE microfilter to prepare a solution forming the composition of the lower layer membrane of the inhibitor.

[0130] (Dissolution test in resist solvent) Solutions of the compositions used to form the resist underlayer film prepared in Comparative Example 1 and Examples 1-12 were coated onto silicon wafers using a spin coater and fired at 240°C, 350°C, or 400°C for 60 seconds on a hot plate to form a resist underlayer film (film thickness 200 nm). These resist underlayer films were then immersed in a widely used diluent with a PGME / PGMEA ratio of 7 / 3 to confirm their solvent resistance (Table 1). A reduction in film thickness of less than 1% after immersion was recorded as ○, and a reduction in film thickness of more than 1% after immersion was recorded as ×.

[0131]

[0132] When fired at 240°C, compared with Comparative Example 1, the Example 1 showed good curing properties, while the Comparative Example 1 showed insufficient curing properties. Therefore, introducing specific crosslinking groups into the polymer greatly improves curing properties. Moreover, except for the case where a general crosslinking agent and catalyst are combined and fired, solvent resistance cannot be obtained by firing at low temperatures. However, as shown in Examples 1-12, due to the presence of specific crosslinking groups in the polymer, sufficient curing properties can be obtained in all cases, whether a crosslinking agent and acid catalyst are used, only an acid catalyst is used, or neither a crosslinking agent nor an acid catalyst is used.

[0133] (Optical Constant Measurement) Solutions of the compositions used in Comparative Example 1 and Examples 1-12 to form the resist underlayer film were coated onto silicon wafers using a spin coater. The wafers were then heated on a hot plate at 240°C, 350°C, or 400°C for 60 seconds to form the resist underlayer film (film thickness 50 nm). The refractive index (n value) and optical absorption coefficient (k value, also known as attenuation coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroelastic ellipsometry (Table 2).

[0134]

[0135] As shown in the examples, the optical constants can be changed by changing the types of compounds to be combined.

[0136] (Determination of Dry Etching Rate) The etchant and etching gas used to determine the dry etching rate are as follows: RIE-200NL (manufactured by SAMUCO): CF4

[0137] Solutions of the compositions used in Comparative Example 1 and Examples 1-12 to form the resist underlayer film were coated onto silicon wafers using a spin coater. The wafers were then heated on a hot plate at 240°C, 350°C, or 400°C for 60 seconds to form the resist underlayer film (film thickness 200 nm). The dry etching rate was measured using CF4 gas as the etching gas, and the dry etching rate ratio for Comparative Example 1 and Examples 1-12 was determined. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (KrF photoresist) (Table 3).

[0138]

[0139] As described in the embodiments, the etching rate can be varied by changing the types of compounds to be combined.

[0140] (Determination of Sublimation Content) The determination of sublimation content was performed using the sublimation content measuring apparatus described in International Publication No. 2007 / 111147. The compositions of the forming inhibitor lower layer films prepared in Comparative Example 1 and Examples 1-12 were respectively coated on silicon wafers and fired at 240°C, 350°C, or 400°C for 60 seconds. The sublimation content was measured when the film thickness reached 200 nm (Table 4). Furthermore, the values ​​recorded in the table are the sublimation content of Examples 1-12 / the sublimation content of Comparative Example 1.

[0141]

[0142] When comparing Comparative Example 1 with Examples 1-12, due to the presence of specific crosslinking groups in the polymer, the amount of sublimation can be significantly reduced in all cases, whether using a crosslinking agent and an acid catalyst, using only an acid catalyst, or not using either a crosslinking agent or an acid catalyst. Furthermore, changing the reacting compound also allows for suppressing the amount of sublimation to a lower level. Therefore, concerns about equipment contamination can be reduced.

[0143] (Hardness Measurement) The compositions for forming the resist underlayer film prepared in Comparative Example 1 and Examples 1-12 were coated onto the above-mentioned substrate and fired at 240°C, 350°C, or 400°C for 60 seconds to form a 200 nm resist underlayer film. The hardness of the resist-cured film was evaluated using a Bruker TI-980 nanometer indenter (triboidentor). Compared with Comparative Example 1, the one with higher hardness was rated as ○ (Table 5).

[0144]

[0145] Comparing Comparative Example 1 with Examples 1-12, due to the presence of specific crosslinking groups in the polymer, the hardness can be increased in all cases: when using a crosslinking agent and an acid catalyst, when using only an acid catalyst, and when neither a crosslinking agent nor an acid catalyst is used. Furthermore, the hardness generally increases with higher firing temperatures. However, the hardness of the Example, fired at a low temperature of 240°C, is higher than that of the Comparative Example, fired at a high temperature of 350°C. Therefore, it is believed that good flexural resistance is observed not only in the high-temperature firing case but also in the low-temperature firing case.

[0146] (Evaluation of Embedding Performance) Embedding performance was confirmed for a dense patterned region with a trench width of 50 nm and a spacing of 100 nm on a SiO2 substrate with a film thickness of 200 nm. The composition for forming the resist underlayer film prepared in Comparative Example 1 and Examples 1-12 was coated onto the above substrate, and then fired at 240°C, 350°C, or 400°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of the substrate was observed using a Hitachi High Technology (S-4800) scanning electron microscope to confirm whether the composition for forming the resist underlayer film was filled within the pattern (Table 6). Those patterns filled with the composition for forming the resist underlayer film were marked ○, and those patterns not filled with the composition for forming the resist underlayer film were marked ×.

[0147]

[0148] The embodiments exhibit the same high embedding properties as conventional materials (= comparative examples).

[0149] (Bending resistance evaluation) Solutions of the compositions for forming the resist underlayer films prepared in Comparative Example 1 and Example 12 were respectively coated onto silicon wafers with a silicon oxide coating using a spin coater. The wafers were heated on a hot plate at 350°C for 60 seconds to form a resist underlayer film (film thickness 200 nm). A silicon hard mask composition solution was coated onto the resist underlayer film, and the wafers were heated at 240°C for 1 minute to form a silicon hard mask layer (film thickness 30 nm). A resist solution was coated onto this mask, and the wafers were heated at 100°C for 1 minute to form a resist layer (film thickness 150 nm). The mask was exposed at a wavelength of 193 nm, and after exposure, the wafers were heated to PEB (at 105°C for 1 minute) and then developed to obtain the resist pattern. Subsequently, dry etching was performed using fluorine-based and oxygen-based gases to transfer the resist pattern onto a silicon wafer coated with a silicon oxide film. The shape of each pattern was then observed using a CG-4100 manufactured by Hitachi High Technology Co., Ltd.

[0150] As the pattern width narrows, bending of irregular patterns is more likely to occur. Because of this, faithful substrate processing cannot be performed. Therefore, bending is less likely to occur, allowing for fine substrate processing (Table 7). Compared to the comparative example, the one with higher bending resistance is rated ○.

[0151]

[0152] Next, the evaluation of using the material of the present invention as a crosslinking agent is as follows. The above-described methods were used for dissolution tests in the resist solvent, determination of optical constants, determination of dry etching rate, and tests of hardness and flexural strength. Furthermore, the coating test and heat resistance evaluation of the step substrate were performed as follows.

[0153] (Coating Test on Step-Difference Substrate) As a coating test on a step-difference substrate, the coating thickness of an unpatterned open region (OPEN) and a dense patterned region (DENSE) with a trench width of 50 nm and a pitch of 100 nm were compared using a 200 nm thick SiO2 substrate. The composition of the resist underlayer film prepared in Comparative Example 2 and Example 13 was coated onto the above substrate and then fired at 350°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of the substrate was observed using a Hitachi High Technology (S-4800) scanning electron microscope. The planarization was evaluated by measuring the difference in film thickness between the trench region (patterned area) and the open region (unpatterned area) of the step-difference substrate (referred to as the deviation of the coating step difference between the trench region and the open region). Here, flatness refers to a smaller difference in film thickness (iso-dense deviation) between the patterned areas (grooved areas (patterned areas)) and the unpatterned areas (open areas (unpatterned areas)) of the coated material on top of them. Compared with Comparative Example 2, the smaller deviation is rated as ○.

[0154] (Heat Resistance Evaluation) Solutions of the compositions used in Comparative Example 2 and Example 13 to form the resist lower layer film were coated onto silicon wafers using a spin coater and fired at 350°C for 60 seconds on a heating plate to form a 200nm resist lower layer film. The resulting films were shaved off and heated from room temperature (approximately 20°C) at a rate of 10°C per minute. Thermogravimetric analysis was performed in atmospheric temperature to confirm the change in weight reduction over time. In the heat resistance evaluation, the films with a weight reduction rate smaller than that of Comparative Example 2 were evaluated as 0.

[0155]

[0156] From the above, when using the material of the present invention as a crosslinking agent, compared with the crosslinking agent of the comparative example, a material with high planarity, high heat resistance, high hardness, and good flexural strength can be produced. [Industrial Applicability]

[0157] According to the present invention, a novel composition for forming an inhibitory underlayer film can be provided, which is due to the requirement that a high-hardness film with high flexural strength can be obtained even without acid catalysts and crosslinking agents, which can self-harden at low temperatures, reduce the amount of sublimation, and can also be used as a crosslinking agent, showing higher planarization and higher heat resistance than conventional crosslinking agents, and the embedding properties are the same as conventional products, and the optical constants and etching resistance can be freely changed by selecting monomers.

Claims

1. A composition for forming a resistive underlayer film comprising a polymer (X) and an organic solvent, wherein the polymer (X) contains repeating units: an aromatic compound A with a ROCH2- group (R being a monovalent organic group, a hydrogen atom, or a mixture thereof) directly bonded to an aromatic ring, and an aromatic compound B having 120 or fewer carbon atoms different from A, wherein the aromatic rings of the aforementioned aromatic compound A and the aromatic rings of the aromatic compound B are only linked by a linker group -O- cross-bonding repeating unit, and the repeating unit is 1 to 6 Bs bonded to 1 A, and the solid fraction of the composition for forming a resistive underlayer film is 0.1 to 70% by mass.

2. A composition for forming an inhibitor underlayer film comprising a polymer (X) and an organic solvent, wherein the polymer (X) comprises repeating units: an aromatic compound A with a ROCH2- group (R being a monovalent organic group, a hydrogen atom, or a mixture thereof) directly bonded to an aromatic ring, and an aromatic compound B having a skeleton with 120 or fewer carbon atoms different from A and having a benzene ring bonded through a single carbon atom, which are repeating units linked by a linker group -O- cross-bonding, and the repeating unit is 1 to 6 Bs bonded to 1 A, wherein the solid fraction of the composition for forming an inhibitor underlayer film is 0.1 to 70% by mass.

3. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the polymer (X) contains repeating structural units represented by formula (1), (in formula (1), A1 represents an organic group of aromatic compound A directly bonded to an aromatic ring by a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and B1 represents an organic group of aromatic compound B with 120 or fewer carbon atoms, which is different from A1).

4. The composition of the forming inhibitor underlayer film as claimed in claim 3, wherein the R group in formula (1) may be substituted with phenyl, naphthyl or anthracene and may be a saturated or unsaturated straight or branched C2-C20 aliphatic or C3-C20 alicyclic hydrocarbon group, hydrogen atom or a mixture thereof, interrupted by oxygen atom, nitrogen atom or carbonyl group.

5. As claimed in the composition of the lower layer film of the inhibitor, wherein B1 in formula (1) is represented by the following formula (2), (in formula (2), C1 and C2 each independently represent an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms, Y represents a single bond, carbonyl, sulfonyl, -CR12- or -(CF3)C(CF3)-, R1 represents a carbon ring that may be interrupted by an oxygen atom, carbonyl, nitrogen atom, carbon-carbon double bond or carbon-carbon triple bond, and the carbon-carbon double bond or carbon-carbon triple bond may be bonded to a terminal alkyl group with 1 to 10 carbon atoms, hydroxyl, hydrogen atom, halogen, aromatic hydrocarbon group with 6 to 20 carbon atoms or -NR22, R2 represents a chain or cyclic alkyl group with 1 to 10 carbon atoms, i is 0 or 1, and the dashed line represents the bond with an oxygen atom).

6. As claimed in claim 5, the composition of the forming inhibitor underlayer film, wherein i in formula (2) is 1.

7. The composition of the forming inhibitor underlayer film as claimed in claim 5, wherein the polymer (X) further contains repeating structural units represented by formula (3), (in formula (3), B1 is represented by the aforementioned formula (2), and A2 represents an organic group derived from an aromatic compound A' with 120 or fewer carbon atoms, which is different from B1).

8. The composition of the forming inhibitor underlayer film as claimed in claim 6, wherein the polymer (X) further contains repeating structural units represented by formula (3), (in formula (3), B1 is represented by the aforementioned formula (2), and A2 represents an organic group derived from an aromatic compound A' with 120 or fewer carbon atoms, which is different from B1).

9. The composition of the lower layer film of the forming inhibitor as claimed in claim 1 or 2, wherein A1 in formula (1) does not have a phenolic hydroxyl group.

10. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the polymer (X) has an aromatic hydrocarbon group having 6 to 30 substituted carbon atoms at at least one end.

11. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the film material (Z) is further capable of crosslinking with the polymer (X).

12. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the forming inhibitor further comprises a crosslinking agent.

13. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the forming inhibitor further comprises an acid and / or an acid generating agent.

14. The composition of the forming inhibitor underlayer film as claimed in claim 1 or 2, wherein the forming inhibitor further comprises a surfactant.

15. The composition of the inhibitor underlayer film as claimed in claim 1 or 2, wherein the aforementioned organic solvent comprises a solvent having a boiling point of 160°C or higher.

16. A resistive underlayer film, characterized in that it is a sintered product of a coated film made of any one of the compositions of claims 1 to 15.

17. A method for manufacturing a semiconductor device, comprising the following steps: forming a resist underlayer film on a semiconductor substrate using any one of the components of claims 1 to 15; forming a resist film on the formed resist underlayer film; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing it; etching the aforementioned resist underlayer film through the formed resist pattern and patterning it; and processing a semiconductor substrate through the patterned resist underlayer film.

18. A method for manufacturing a semiconductor device, comprising the following steps: forming a resist underlayer film on a semiconductor substrate using a composition of any one of claims 1 to 15; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing it; etching the hard mask through the formed resist pattern and patterning it; etching the resist underlayer film through the patterned hard mask and patterning it; and processing a semiconductor substrate through the patterned resist underlayer film.

19. A method for manufacturing a semiconductor device as claimed in claim 17 or 18, wherein the step of forming a resist underlayer film is performed by nanoimprint lithography.