Resist underlayer film-foming composition

Abstract

A resist underlayer film-forming composition capable of forming a resist underlayer film, the etching resistance of which can be enhanced by plasma treatment or ion implantation treatment, the composition comprising: a resin (A) having an aromatic hydrocarbon ring; and a solvent (B), the resin (A) being at least one from among a vinyl resin, a polyester resin, a polyether resin, a resin having an ether bond or an ester bond in its side chain, a polyimide resin, and a polyamide resin.

Description

Composition for forming resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a method for producing a resist underlayer film, a method for producing a semiconductor device, and a method for forming a resist pattern.

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, the integration density of semiconductor devices has increased, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to influences from the semiconductor substrate and the like has become a major problem. To address this issue, methods of providing a resist underlayer film between the resist and the semiconductor substrate have been widely investigated.

[0003] Patent Document 1 discloses a composition for forming an underlayer film for lithography, which contains a naphthalene ring having a halogen atom. Patent Document 2 discloses a halogenated antireflective film. Patent Document 3 discloses a composition for forming a resist underlayer film.

[0004] In this technical situation, a method for modifying the surface of a film using plasma is known. For example, Patent Document 4 discloses a technique for producing a cured film by irradiating a conductive polymer precursor such as polythiophene with plasma to polymerize it, in order to obtain a film having excellent heat resistance and moisture resistance.

[0005] International Publication No. 2006 / 003850 Special Publication No. 2005-526270 International Publication No. 2020 / 111068 Japanese Patent No. 5746670

[0006] Properties required for a resist underlayer film include, for example, no intermixing with a resist film formed on top (being insoluble in a resist solvent), excellent etching resistance, etc. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film that can form a resist underlayer film having excellent etching resistance, as well as a method for manufacturing a resist underlayer film, a method for manufacturing a semiconductor device, and a method for forming a resist pattern that use the composition for forming a resist underlayer film.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention encompasses the following aspects. [1] A composition for forming a resist underlayer film, capable of forming a resist underlayer film that can be subjected to a plasma treatment or an ion implantation treatment to enhance etching resistance, comprising: a resin (A) having an aromatic hydrocarbon ring; and a solvent (B), wherein the resin (A) is at least one of a vinyl resin, a polyester resin, a polyether resin, a resin having an ether bond or an ester bond in a side chain, a polyimide resin, and a polyamide resin. [2] The composition for forming a resist underlayer film according to [1], wherein the resin (A) comprises the vinyl resin, and the vinyl resin comprises at least a resin having a structural unit represented by the following formula (A-1): (In formula (A-1), R １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; X ０ represents a single bond, —COO—, or —CONH—; L ０ represents a monovalent organic group having an aromatic hydrocarbon ring.) [3] The composition for forming a resist underlayer film according to [1], wherein the resin (A) includes the polyester-based resin or the polyether-based resin, and the polyester-based resin and the polyether-based resin include a resin having at least one of a resin having a structural unit represented by the following formula (A-2) and a resin having a structural unit represented by the following formula (A-3): (In formula (A-2), each A independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ and Q ２ each independently represents a divalent organic group; １ and Q ２ Both or either one of X has an aromatic hydrocarbon ring; １ ~X ４ each independently represents a single bond, an ether bond, or an ester bond. (In formula (A-3), T ３ represents a group having a monocyclic aliphatic ring constituting the main chain, and Q ３ represents a divalent linking group, Ar ３ represents an aromatic hydrocarbon ring which may have a substituent.) [4] The composition for forming a resist underlayer film according to [1], wherein the resin (A) includes a resin having an ether bond or an ester bond in a side chain, and the resin having an ether bond or an ester bond in a side chain includes a resin having at least a structural unit represented by the following formula (A-4): (In formula (A-4), Ar ４ represents an optionally substituted benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring; L ５ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group, and m5 represents an integer of 0 to 5. When m5 is 2 to 5, multiple L ５ may be the same or different. ４ represents a divalent organic group constituting the main chain, and Q ４ represents a divalent linking group having an ether bond or an ester bond, and Q ５represents a monovalent organic group which may have a substituent. k represents an integer of 1 to 3. [5] The composition for forming a resist underlayer film according to any one of [1] to [4], wherein the solvent (B) contains at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether. [6] The composition for forming a resist underlayer film according to any one of [1] to [5], further containing at least one selected from the group consisting of an acid, a salt thereof, and an acid generator. [7] The composition for forming a resist underlayer film according to any one of [1] to [6], further containing a crosslinking agent. [8] The composition for forming a resist underlayer film according to any one of [1] to [7], further containing a surfactant. [9] The composition for forming a resist underlayer film according to any one of [1] to [8], wherein the etching resistance of the resist underlayer film after the plasma treatment is at least 1.01 times that of the resist underlayer film before the plasma treatment.

[10] The composition for forming a resist underlayer film according to any one of [1] to [8], wherein the etching resistance of the resist underlayer film after the ion implantation treatment is at least 1.01 times that of the resist underlayer film before the ion implantation treatment.

[11] A method for producing a resist underlayer film, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[10] , and treating the coating film with plasma or ion implantation to form a resist underlayer film.

[12] A method for forming a resist pattern used in semiconductor production, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[10] , and treating the coating film with plasma or ion implantation to form a resist underlayer film.

[13] A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[10] ; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[14] A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[10] ; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[15] A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[10] ; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing a semiconductor substrate through the patterned resist underlayer film.

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

[10] ; subjecting the coating film to a plasma treatment or ion implantation treatment to form a resist underlayer film; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film on the resist underlayer film after removing the hard mask; processing the vapor-deposited film by etching; removing the patterned resist underlayer film to leave a patterned vapor-deposited film; and processing a semiconductor substrate through the patterned vapor-deposited film.

[17] The method for manufacturing a semiconductor device according to any one of

[14] to

[16] , wherein the hard mask is formed by applying a composition containing an inorganic substance or vapor-depositing an inorganic substance.

[18] The method for manufacturing a semiconductor device according to any one of

[13] to

[17] , wherein the resist film is patterned by a nanoimprint method or a self-assembled film.

[19] The method for manufacturing a semiconductor device according to

[15] or

[16] , wherein the hard mask is removed by etching or an alkaline chemical solution.

[0009] According to the present invention, it is possible to provide a composition for forming a resist underlayer film that can form a resist underlayer film having excellent etching resistance, as well as a method for producing a resist underlayer film, a method for producing a semiconductor device, and a method for forming a resist pattern, all of which use the composition for forming a resist underlayer film.

[0010] (Composition for forming resist underlayer film) The composition for forming resist underlayer film of the present invention is a composition capable of forming a resist underlayer film having enhanced etching resistance by plasma treatment or ion implantation treatment. In this specification, "enhancing etching resistance" means that the etching resistance of the resist underlayer film after plasma treatment or ion implantation treatment is 1.01 times or more higher than the etching resistance of the resist underlayer film before plasma treatment or ion implantation treatment. The etching resistance of the resist underlayer film before plasma treatment or ion implantation treatment and the etching resistance of the resist underlayer film after plasma treatment or ion implantation treatment can be determined, for example, by calculating the difference in film thickness between the resist underlayer film before and after etching. The film thickness of the resist underlayer film can be determined by observation with a scanning electron microscope (SEM), film thickness measurement using an optical system, or the like.

[0011] The etching resistance of the resist underlayer film after the plasma treatment relative to the etching resistance of the resist underlayer film before the plasma treatment is preferably 1.01 times or more, more preferably 1.05 times or more, and even more preferably 1.10 times or more. The upper limit of the etching resistance of the resist underlayer film after the plasma treatment relative to the etching resistance of the resist underlayer film before the plasma treatment is not particularly limited, but is, for example, 5.0 times. The etching resistance of the resist underlayer film after the ion implantation treatment relative to the etching resistance of the resist underlayer film before the ion implantation treatment is preferably 1.01 times or more, more preferably 1.05 times or more, and even more preferably 1.10 times or more. The upper limit of the etching resistance of the resist underlayer film after the ion implantation treatment relative to the etching resistance of the resist underlayer film before the ion implantation treatment is not particularly limited, but is, for example, 5.0 times.

[0012] The composition for forming a resist underlayer film of the present invention contains a resin (A) having an aromatic hydrocarbon ring and a solvent (B). The composition for forming a resist underlayer film may contain an acid, an acid salt, an acid generator, a crosslinking agent, a surfactant, etc. The composition for forming a resist underlayer film contains the resin (A) having an aromatic hydrocarbon ring, and by subjecting it to a plasma treatment or an ion implantation treatment, the etching resistance of the resist underlayer film can be increased.

[0013] <Resin (A)> The resin (A) is at least one of a vinyl resin, a polyester resin, a polyether resin, a resin having an ether bond or an ester bond in a side chain, a polyimide resin, and a polyamide resin. Examples of the vinyl resin include a polystyrene resin, a polyacrylic resin, a polymethacrylic resin, and a polyacrylamide resin. Examples of the polyamide resin include a polyamide and a polyamic acid. The resin (A) is preferably a vinyl resin, a polyester resin, a polyether resin, or a resin having an ether bond or an ester bond in a side chain. Furthermore, the resin (A) preferably does not contain a novolac resin that does not have an ether bond or an ester bond in a side chain. These resins may be used alone or in combination of two or more. The resin may be a polymer, an oligomer, or a low molecular weight compound.

[0014] <<Resin (A-1)>> The resin (A) preferably contains at least a resin having a structural unit represented by the following formula (A-1) (hereinafter also referred to as "resin (A-1)"). The resin (A-1) corresponds to a vinyl-based resin. As will be described later, the resin (A-1) may be a homopolymer having one type of structural unit, or a copolymer having two or more types of structural units.

[0015]

[0016] (In formula (A-1), R １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; X ０ represents a single bond, —COO—, or —CONH—; L ０ represents a monovalent organic group having an aromatic hydrocarbon ring.

[0017] R １ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １ Examples of the monovalent organic group having 1 to 20 carbon atoms in R include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. １The monovalent organic group having 1 to 20 carbon atoms in the formula (I) may be substituted with a hydroxy group or may be interrupted at one or more positions by a heteroatom. Examples of heteroatoms include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of alkyl groups having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, and an n-icosyl group. These alkyl groups may be linear, branched, or cyclic. Examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-dodecenyl, 1-tetradecenyl, 1-hexadecenyl, 1-octadecenyl, and 1-icosenyl. These alkenyl groups may be linear, branched, or cyclic. Examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, 1-decynyl, 1-dodecynyl, 1-tetradecynyl, 1-hexadecynyl, 1-octadecynyl, and 1-icosynyl groups. These alkynyl groups may be linear, branched, or cyclic. Examples of alkynyl groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy, phenoxy, benzyloxy, and 1-naphthyloxy groups. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, an o-xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a chrysenyl group, a triphenylenyl group, and a pyrenyl group.

[0018] L ０ Examples of the monovalent organic group in L include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group formed by combining any of these with one or more selected from a carbonyl group, an ether group, a thioether group, and an amino group. ０ The monovalent organic group in L has an aromatic hydrocarbon ring. ０ At least one hydrogen atom of the monovalent organic group is substituted with a group having an aromatic hydrocarbon ring. Examples of such groups having an aromatic hydrocarbon ring include a phenyl group, a tolyl group, an o-xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a chrysenyl group, a triphenylenyl group, and a pyrenyl group.

[0019] Resin (A-1) preferably contains a resin having at least one of a structural unit represented by formula (A-1a) below, a structural unit represented by formula (A-1b) below, and a structural unit represented by formula (A-1c) below. Resin (A-1) may be a homopolymer or copolymer of these structural units. Furthermore, resin (A-1) may contain at least these structural units, and may also be a copolymer of these structural units with other structural units.

[0020] (In formula (A-1a), R １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; Ar １ represents a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring; L １ represents a hydroxy group, a cyano group, a nitro group, an amino group, an alkylamino group, a carboxy group, a formyl group, an acyl group, a sulfonyl-containing group, an ether bond-containing group, a thiol group, or an ester group; L ２represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and the hydrogen atoms of these aryl groups may be substituted with an alkyl group, an alkenyl group, or an alkynyl group, and the carbon-carbon bond of these substituted alkyl groups, alkenyl groups, or alkynyl groups may be interrupted by an oxygen atom. m1 represents an integer of 0 to 3. m2 represents an integer of 0 to 5, with the proviso that the sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L １ may be the same or different. When m2 is 2 to 5, multiple L ２ may be the same or different. １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; L ３ represents a hydrogen atom or a monovalent group. １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; L ４ represents a hydrogen atom or a monovalent group.

[0021] L １ The alkylamino group in the formula (I) is —NHR or —NR ２ Here, R is a saturated or unsaturated, linear, branched or cyclic hydrocarbon group (-R ａ ) represents. ａ Examples of the —NR include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ２ In the formula, the two R's may be the same or different. １ The acyl group in the formula (I) includes a group represented by -COR, where R is the hydrocarbon group -R ａ or a halogen atom. １ The sulfonyl-containing group in ２R is a hydrocarbon group, which may be substituted with a hydroxy group or a halogen atom, -R ａ , an alkylamino group, or a hydroxy group. １ The ether bond-containing group in R １１ -O-R １１ In this case, R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group or a pyrenyl group. The ether bond-containing group may be, for example, an organic group containing an ether bond, such as a methoxy group, an ethoxy group or a phenoxy group, or an organic group containing an epoxy group or an oxetane group. １ The ester group in the formula (I) is —CO ２ Examples of the hydrocarbon group include a group represented by -R or -OCOR, where R is a hydroxy group or a group optionally substituted with a halogen atom. ａ Represents.

[0022] L ２ The halogen atom, alkyl group, alkenyl group, and alkynyl group in R １ The halogen atoms, alkyl groups, alkenyl groups, and alkynyl groups in L are examples of atoms or groups similar to those in L. ２ Examples of the alkoxy group having 1 to 10 carbon atoms in the formula (I) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, an allyloxy group, a cyclohexyloxy group, a phenoxy group, a benzyloxy group, and a 1-naphthyloxy group. m1 represents an integer of 0 to 3 and may be 0, 1, 2, or 3. m2 represents an integer of 0 to 5 and may be 0, 1, 2, 3, 4, or 5.

[0023] L in formula (A-1b) ３Examples of the monovalent group include a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylamino group, an isocyanate group, an alkylisocyanate group, a carboxy group, a formyl group, an acyl group, a sulfonyl-containing group, an ether bond-containing group, a thiol group, an ester group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ３ One or more hydrogen atoms in the monovalent group may be substituted with a substituent. Examples of such a substituent include a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylamino group, an isocyanate group, an alkylisocyanate group, a carboxy group, a formyl group, an acyl group, a sulfonyl-containing group, an ether bond-containing group, a thiol group, an ester group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ３ The monovalent group may be interrupted by one or more atoms or groups selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group, or may form a ring structure bonded by one or more atoms or groups selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group.

[0024] L ３ The alkyl isocyanate group in the monovalent group may be a group represented by -RNCO, where R is the hydrocarbon group -R which may be substituted with a hydroxy group or a halogen atom. ａ Represents.

[0025] L in formula (A-1c) ４ represents L in formula (A-1b). ３ is the same as:

[0026] Also, L ３ Examples of the group include a group represented by the following formula (A-1b-1).

[0027]

[0028] (In formula (A-1b-1), X １０ represents a single bond or a carbonyl group, L ３ａ represents a monovalent group. * represents a bond.

[0029] L ３ａ The monovalent group in the formula (A-1b) is L ３ and the like.

[0030] Examples of the monomers used to derive formula (A-1a) include the following compounds: １ represents a hydrogen atom or a methyl group.

[0031]

[0032] Examples of the monomers used to derive formula (A-1b) include the following compounds: １ represents a hydrogen atom or a methyl group.

[0033]

[0034] Examples of the monomers used to derive formula (A-1c) include the following compounds: １ represents a hydrogen atom or a methyl group.

[0035]

[0036] Resin (A-1) may be a homopolymer having one type of structural unit, or may be a copolymer having two or more types of structural units. Resin (A-1) may have an aromatic hydrocarbon ring anywhere in its structure. For example, it may have only the structural unit represented by formula (A-1a), or it may have a structural unit represented by formula (A-1a) and a structural unit represented by formula (A-1b), or it may have a structural unit represented by formula (A-1a) and a structural unit represented by formula (A-1c), or it may have a structural unit represented by formula (A-1a), a structural unit represented by formula (A-1b), and a structural unit represented by formula (A-1c). When the structural unit represented by formula (A-1b) has an aromatic hydrocarbon ring, Resin (A-1) may have only the structural unit represented by formula (A-1b), or it may have a structural unit represented by formula (A-1b) and a structural unit represented by formula (A-1c). When the structural unit represented by formula (A-1c) has an aromatic hydrocarbon ring, the resin (A-1) may have only the structural unit represented by formula (A-1c), or may have both the structural unit represented by formula (A-1c) and the structural unit represented by formula (A-1b).

[0037] The proportion of the structural unit represented by formula (A-1a), the structural unit represented by formula (A-1b), or the structural unit represented by formula (A-1c) in resin (A-1) is not particularly limited, but the molar ratio of the structural unit represented by formula (A-1a), the structural unit represented by formula (A-1b), or the structural unit represented by formula (A-1c) relative to all structural units in resin (A-1) may be, for example, 5 mol % or more and 100 mol % or less, or 5 mol % or more and less than 100 mol %.

[0038] Resin (A-1) may contain structural units other than the structural unit represented by formula (A-1a), the structural unit represented by formula (A-1b), or the structural unit represented by formula (A-1c). In this case, the molar ratio of the other structural units to all structural units of resin (A-1) is, for example, preferably more than 0 mol% and 90 mol% or less, more than 0 mol% and 80 mol% or less, more than 0 mol% and 70 mol% or less, more than 0 mol% and 60 mol% or less, more than 0 mol% and 50 mol% or less, more than 0 mol% and 40 mol% or less, more than 0 mol% and 30 mol% or less, more than 0 mol% and 20 mol% or less, more than 0 mol% and 10 mol% or less, more than 0 mol% and 5 mol% or less, or more than 0 mol% and 1 mol% or less.

[0039] Examples of resin (A-1) include polymers described in WO 2015 / 178235, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0040] The molecular weight of the resin (A-1) is not particularly limited. The lower limit of the weight average molecular weight of the resin (A-1) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight average molecular weight of the resin (A-1) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0041] <<Resin (A-2)>> The resin (A) preferably contains a resin having a structural unit represented by the following formula (A-2) (hereinafter also referred to as "resin (A-2)") The resin (A-2) corresponds to a polyester-based resin or a polyether-based resin.

[0042] (In formula (A-2), each A independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ and Q ２ each independently represents a divalent organic group; １ and Q ２ Both or either one of X has an aromatic hydrocarbon ring; １ ~X ４ each independently represents a single bond, an ether bond, or an ester bond.

[0043] Q１ and Q ２ The number of carbon atoms in X is not particularly limited, and may be, for example, 1 to 50, 3 to 40, or 6 to 30. １ ~X ４ When is an ester bond, X １ and X ３ is preferably —OCO—, and X ２ and X ４ is preferably —COO—.

[0044] Q １ and Q ２ Examples of the divalent organic group include alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, alkynylene groups having 2 to 20 carbon atoms, and aryl groups having 6 to 50 carbon atoms. At least one hydrogen atom of these organic groups may be substituted with a substituent. Examples of the substituent include halogen atoms, hydroxy groups, cyano groups, nitro groups, amino groups, alkylamino groups, isocyanate groups, alkylisocyanate groups, carboxy groups, formyl groups, acyl groups, sulfonyl-containing groups, ether-bond-containing groups, thiol groups, ester groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. In addition, Q １ and Q ２ The divalent organic group may be separated by one or more atoms or groups selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group, may be branched, or may form a ring structure bonded by one or more atoms or groups selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group.

[0045] From the viewpoint of suitably obtaining the effects of the present invention, Q in formula (A-2) １ In order to obtain the effects of the present invention, Q in formula (A-2) is preferably represented by the following formula (A-2-1). ２ is preferably represented by any one of the following formula (A-2-2a), (A-2-2b), and (A-2-2c).

[0046] (In formula (A-2-1) and formulas (A-2-2a) to (A-2-2c), R ａ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group. W is a single bond, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -CO-, -O-, -S- or SO ２ Each m independently represents an integer of 0 to 2. Each n independently represents an integer of 0 to 4. * represents a bond.

[0047] Examples of the alkyl group having 1 to 20 carbon atoms include the alkyl groups described in <<Resin (A-1)>>.

[0048] Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, and 1-methyl-3-butenyl. nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl Examples of the cyclopentyl group include an aryl group, a 1-i-propyl-2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group.

[0049] Examples of the alkynyl group having 2 to 10 carbon atoms include the above-mentioned alkenyl groups in which the carbon-carbon double bond is replaced with a carbon-carbon triple bond.

[0050] Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n -pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, cyclopentyloxy group, cyclohexyloxy group, norbornyoxy group, adamantyloxy group, and the like.

[0051] Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, o-xylyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, chrysenyl, triphenylenyl, and pyrenyl groups. Examples of aryloxy groups having 6 to 30 carbon atoms include phenoxy, benzyloxy, and 1-naphthyloxy groups. Examples of hydroxyalkyl groups having 1 to 20 carbon atoms include groups in which at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms has been substituted with a hydroxy group. Examples of ester groups include -CO ２ In this case, R is a hydrocarbon group, which may be substituted with a hydroxy group or a halogen atom, and a group represented by -R ａ The amide group is —NHCOR, —CONHR, —NRCOR, or —CONR ２In this case, R is a hydrocarbon group -R ａ When there are two R's, the two R's may be the same or different. The sulfonyl-containing group includes -SO ２ R is a hydrocarbon group, which may be substituted with a hydroxy group or a halogen atom, ａ , alkylamino group, or hydroxy group. Examples of sulfide-containing groups include groups represented by -SR, where R is a hydroxy group, a hydrocarbon group -R which may be substituted with a halogen atom, or ａ The ether bond-containing group is represented by R １１ -O-R １１ In this case, R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group or a pyrenyl group. The ether bond-containing group may be, for example, an organic group containing an ether bond, such as a methoxy group, an ethoxy group or a phenoxy group, or an organic group containing an epoxy group or an oxetane group.

[0052] From the viewpoint of more suitably achieving the effects of the present invention, m in formula (A-2-1) is preferably 0 or 1. From the viewpoint of more suitably achieving the effects of the present invention, m in formula (A-2-2a) is preferably 0 or 1, and more preferably 0.

[0053] In order to more suitably obtain the effects of the present invention, n in formula (A-2-1) and formulas (A-2-2a) to (A-2-2c) is preferably each independently an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0054] R ａ As the alkyl group, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms are preferred.

[0055] Q in formula (A-2) １ and Q ２ The structure may be represented by the following formula (A-2-3).

[0056] (In formula (A-2-3), X １１ represents a divalent group represented by any one of the following formulas (A-2-3a) to (A-2-3d). * represents a bond.

[0057] (In formulas (A-2-3a) to (A-2-3d), R １ ~R ７ R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and at least one hydrogen atom of the benzyl group or phenyl group may be substituted by at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ and R ４ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom in formula (A-2-3). *2 represents a bond bonded to a nitrogen atom in formula (A-2-3).

[0058] The structure represented by formula (A-2-3) is, for example, a structure derived from cyanuric acid, a structure derived from hydantoin, or a structure derived from uracil.

[0059] Q in formula (A-2) １ or Q ２ Examples of the structure include the following: In the formula, * represents a bond.

[0060]

[0061] The resin (A-2) may further have a monovalent group represented by the following formula (E): The monovalent group represented by formula (E) is located, for example, at the terminal of the resin (A-2).

[0062] (In formula (E), p represents 0 or 1. Z represents a monovalent group having 1 to 20 carbon atoms. * represents a bond.)

[0063] Z is R in formula (A-1) of the above-mentioned <<Resin (A-1)>> １ Examples of the monovalent organic groups having 1 to 20 carbon atoms include those shown in the formula (1). The number of carbon atoms in Z is preferably 6 to 20. Z has, for example, an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. For example, in formula (E), Z has an aromatic hydrocarbon ring, and a carbon atom constituting the aromatic hydrocarbon ring is bonded to the carbonyl carbon atom in formula (E).

[0064] Examples of Z in formula (E) include groups represented by the following formula (E-1).

[0065] (In formula (E-1), q represents an integer of 0 to 2. r represents an integer of 0 to 4. R ｂ each independently represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. * represents a bond.

[0066] Examples of the monovalent group represented by formula (E) include the following groups.

[0067] * represents a bond.

[0068] Resin (A-2) can be synthesized, for example, by the following method: (I): Reaction of a compound represented by the following formula (1A) with a compound represented by the following formula (1B). (II): Reaction of a compound represented by the following formula (1A), a compound represented by the following formula (1B), and a compound represented by the following formula (EA). (In formula (1A), Q １ , X１ and X ２ is Q in formula (A-2) １ , X １ and X ２ In formula (1B), A and Q ２ , X ３ and X ４ are A and Q in formula (1). ２ , X ３ and X ４ In formula (EA), p and Z have the same meanings as p and Z in formula (E), respectively.

[0069] The above reaction may be carried out in the presence of a catalyst, for example. Examples of the catalyst include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10 mass% based on the total mass of the reaction raw materials used in the reaction. Optimal reaction temperature and time can be selected from the ranges of, for example, 50 to 160°C and 2 to 50 hours.

[0070] Some examples of compounds represented by formula (1B) include the structures shown below.

[0071]

[0072] The weight average molecular weight of the resin (A-2) is not particularly limited, but is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, and particularly preferably from 2,500 to 15,000.

[0073] <<Resin (A-3)>> The resin (A) preferably contains a resin having a structural unit represented by the following formula (A-3) (hereinafter also referred to as "resin (A-3)"): The resin (A-3) corresponds to a polyether-based resin.

[0074] (In formula (A-3), T ３ represents a group having a monocyclic aliphatic ring constituting the main chain, and Q３ represents a divalent linking group, Ar ３ represents an aromatic hydrocarbon ring which may have a substituent.

[0075] Resin (A-3) is a compound represented by the formula (A-3) ３ The structural unit may have two or more different structural units represented by formula (A-3).

[0076] Examples of monocyclic aliphatic rings include cycloalkane rings having 4 to 10 carbon atoms. Among these, a cyclohexane ring is preferred.

[0077] The monocyclic aliphatic ring is -Q in formula (A-3). ３ -Ar ３ Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group.

[0078] Examples of alkyl groups having 1 to 20 carbon atoms include the alkyl groups exemplified in <<Resin (A-1)>>. Examples of alkenyl groups having 2 to 10 carbon atoms include the alkenyl groups exemplified in <<Resin (A-1)>>. Examples of alkynyl groups having 2 to 10 carbon atoms include the alkynyl groups exemplified in <<Resin (A-1)>>. Examples of alkoxy groups having 1 to 20 carbon atoms include the alkoxy groups exemplified in <<Resin (A-1)>>.

[0079] Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0080] Examples of the aryloxy group having 6 to 30 carbon atoms, the hydroxyalkyl group having 1 to 20 carbon atoms, the ester group, the amide group, the sulfonyl-containing group, the sulfide-containing group, and the ether bond-containing group include the groups exemplified in <<Resin (A-2)>>.

[0081] The structural unit represented by formula (A-3) is preferably a structural unit represented by the following formula (Xa):

[0082] (In formula (Xa), R ３ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group. ３ represents a divalent linking group. ３ represents an aromatic hydrocarbon ring which may have a substituent.

[0083] Ar in formula (A-3) and formula (Xa) ３ The aromatic hydrocarbon ring in may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.

[0084] Ar in formula (A-3) and formula (Xa) ３Examples of the substituent that may be included include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group.

[0085] Q in formula (A-3) and formula (Xa) ３ The number of atoms constituting the divalent linking group in the formula (I) may be, for example, 1 to 60.

[0086] Q ３ Examples of the linking group include the following linking group (Qa).

[0087] (In formula (Qa), X ５ represents a single bond or a carbonyl group. *1 represents a bond bonding to a monocyclic aliphatic ring. *2 represents a bond bonding to an aromatic hydrocarbon ring.

[0088] The resin (A-3) is, for example, a reaction product of a polymer (X1) having a repeating unit represented by the following formula (X1) and an aromatic carboxylic acid (X2) or a phenol compound (X3).

[0089] (In formula (X1), R ３ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group.

[0090] The polymer having a repeating unit represented by formula (X1) may be a commercially available product, such as EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

[0091] Examples of the aromatic carboxylic acid (X2) include monocyclic aromatic carboxylic acids and fused-ring aromatic carboxylic acids. Examples of the monocyclic aromatic carboxylic acids include benzoic acid. Examples of the fused-ring aromatic carboxylic acids include naphthalenecarboxylic acid and anthracenecarboxylic acid. Examples of the phenol compound (X3) include any compound having a phenolic hydroxyl group, such as phenol, 1-naphthol, 2-naphthol, anthracen-1-ol, anthracen-2-ol, anthracen-9-ol, and 1-hydroxypyrene.

[0092] Examples of the resin (A-3) include the following polymers (X-1) to (X-13): The following polymers have two, three, or four types of repeating units.

[0093] Resin (A-3) includes polymers described in WO 2011 / 021555, the contents of which are incorporated herein by reference to the same extent as if set forth in full.

[0094] The weight average molecular weight of the resin (A-3) is not particularly limited, but is preferably from 1,000 to 15,000, more preferably from 1,500 to 10,000, and particularly preferably from 2,000 to 7,000.

[0095] <<Resin (A-4)>> Resin (A) preferably contains at least a resin having a structural unit represented by the following formula (A-4) (hereinafter also referred to as "resin (A-4)"). Resin (A-4) corresponds to a resin having an ether bond or an ester bond in a side chain. Resin (A-4) may be a homopolymer having one type of structural unit, or may be a copolymer having two or more types of structural units.

[0096] (In formula (A-4), Ar ４ represents an optionally substituted benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring; L ５ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group, and m5 represents an integer of 0 to 5. When m5 is 2 to 5, multiple L ５ may be the same or different. ４ represents a divalent organic group constituting the main chain, and Q ４ represents a divalent linking group having an ether bond or an ester bond, and Q ５ represents a monovalent organic group which may have a substituent; and k represents an integer of 1 to 3.

[0097] Ar ４ Examples of the substituent that may be included include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group.

[0098] T ４ Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an ether bond-containing group, -CO-, -COO-, -NHCO-, or a group consisting of a combination of two or more of these groups. ４ The divalent organic group also includes a group in which a methylene group and an aryl group are combined, a group in which a methine group and an aryl group are combined, a group containing an alicyclic hydrocarbon, and a quaternary carbon atom in a derivative containing a fluorene structure.

[0099] T ４ The alkylene group may be a straight-chain, branched, or cyclic alkylene group.

[0100] T ４Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 1-ethyl-n-propylene group. , cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2, 2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group , 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples of such cyclopropylene groups include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0101] In this specification, the term "alkenylene group" refers to a divalent group generated by losing two hydrogen atoms from an aliphatic hydrocarbon having one carbon-carbon double bond in the molecule, and generally refers to an -C ｎ H ２ｎ－２ The alkenylene group having 2 to 20 carbon atoms means a linear, branched or cyclic alkenylene group containing 2 to 20 carbon atoms, and is represented by -CH=CH-, -CH=CHCH ２ -, -(CH ３ ) C=CH- and the like.

[0102] In this specification, the term "alkynylene group" refers to a divalent group generated by losing two hydrogen atoms from an aliphatic hydrocarbon having one carbon-carbon triple bond in the molecule, and generally refers to a group represented by -C ｎ H ２ｎ－４ The alkynylene group having 2 to 20 carbon atoms means a linear, branched or cyclic alkynylene group containing 2 to 20 carbon atoms, and is represented by -CH≡CH-, -C≡C-CH ２ -, -(CH ２ ) ２ Examples include -C≡C-.

[0103] T ４At least one hydrogen atom of the divalent organic group may be substituted with a substituent. Examples of such substituents include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, hydroxy groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxy groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, and ether bond-containing groups. The number of substituents may be one or more. When there are multiple substituents, the multiple substituents may be the same or different.

[0104] Q ５ Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. ５ At least one hydrogen atom of the monovalent organic group may be substituted with a substituent. ５ Examples of the substituent that may be included include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group.

[0105] Q ４ Examples of the linking group (Qb) include the following linking group (Qb).

[0106] (In formula (Qb), X ６ represents a single bond or a carbonyl group. ４*2 represents a bond to Q in formula (A-4). ５ represents a bond with .)

[0107] The resin (A-4) may be one type or a combination of two or more types. For example, Ar ４ It may be a copolymer having a plurality of structural units of the same type, for example, Ar ４ has a structural unit containing a benzene ring and a structural unit containing a naphthalene ring, ４ Copolymers having a plurality of structural units of different types are not excluded from the technical scope of the present application.

[0108] In formula (A-4), k is an integer of 1 to 3, for example, Ar ４ The ring represented by -Q ４ -Q ５ The number of groups represented by the following formula (I) may be not only one but also two or three.

[0109] Resin (A-4) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (A-4-1) with a carboxylic acid or a phenol compound.

[0110] (In formula (A-4-1), Ar ４ , L ５ , m5, k, and T ４ represents Ar in formula (A-4). ４ , L ５ , m5, k, and T ４ and E is a group having an epoxy group.

[0111] Examples of carboxylic acids include carboxylic acids having 1 to 20 carbon atoms. Examples of carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, capric acid, stearic acid, oleic acid, and linoleic acid. Examples of aromatic carboxylic acids include monocyclic aromatic carboxylic acids and fused ring aromatic carboxylic acids. Examples of monocyclic aromatic carboxylic acids include benzoic acid. Examples of fused ring aromatic carboxylic acids include naphthalenecarboxylic acid and anthracenecarboxylic acid.

[0112] The phenol compound is not particularly limited as long as it has a phenolic hydroxyl group, and examples of the phenol compound include phenol, 1-naphthol, 2-naphthol, anthracen-1-ol, anthracen-2-ol, anthracen-9-ol, and 1-hydroxypyrene.

[0113] The carboxylic acid or phenol compound may have a substituent, such as a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group.

[0114] Resin (A-4) is not particularly limited as long as it satisfies the structural unit of formula (A-4-1). Resins produced by known methods may be used. Commercially available products may also be used. Examples of commercially available products include 1032H60, 157S70, 1031S, and YX7700 (all manufactured by Mitsubishi Chemical Corporation), EPPN-201, EOCN-104S, EOCN-103S, EOCN-102S, EOCN-1020, EOCN-1020-70, EOCN-1020-55, NC-2000-L, NC-3000, NC-3000-L, NC-3000-H, and N C-3000FH-75M, NC-3100, NC-7000L, NC-7000H, NC-3500, NC-7300-L, XD-1000, XD-1000-H, XD-1000-2L , EPPN-502H, EPPN-502HY, EPPN-501H, EPPN-503, FAE-2500, CER-1020, CER-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), EP ICLON (registered trademark) series (HP-5000, HP-7200, HP-6000, HP-9900-75M, HP-7241, N-660, N-665, N-670, N-673, N-680, N-695, N-655-EXP-S, N-662-EXP-S, N-665-EXP, N-665-EXP-S, N-672-EXP, N-670-EXP-S, N-685 -EXP-S, N-673-80M, N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N-865, N-865-80M, TSR-960, TSR-601, 1650-75MPX, EXA-850CRP, 840-S, 850-S, 860, 1055) (all manufactured by DIC Corporation).

[0115] Examples of polymers having a structural unit represented by formula (A-4-1) are shown below.

[0116]

[0117] The weight average molecular weight of the resin (A-4) is not particularly limited, but is preferably from 800 to 20,000, more preferably from 900 to 15,000, and particularly preferably from 1,000 to 10,000.

[0118] The content of the resin (A) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 30% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 60% by mass to 85% by mass, based on the film-constituting components in the composition for forming a resist underlayer film. The film-constituting components refer to components other than the solvent in the composition for forming a resist underlayer film.

[0119] <Solvent (B)> Examples of the solvent (B) include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate. methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate,Propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyrate Examples of suitable solvents include methyl acetoacetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents (B) can be used alone or in combination of two or more.

[0120] Also, solvents with boiling points of 160°C or higher can be included in combination with solvents with boiling points below 160°C.

[0121] As such a high-boiling point solvent, for example, the following compounds described in WO 2018 / 131562 (A1) can be preferably used.

[0122] [R in formula (i)] １ , R ２ and R ３each represent a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and may be the same or different from each other and may be bonded to each other to form a ring structure.] Alternatively, 1,6-diacetoxyhexane (boiling point 260°C) and tripropylene glycol monomethyl ether (boiling point 242°C) described in JP-A No. 2021-84974, as well as various other high-boiling point solvents described in paragraph 0082 of the same publication, can be preferably used.

[0123] Alternatively, dipropylene glycol monomethyl ether acetate (boiling point 213°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol dimethyl ether (boiling point 171°C), dipropylene glycol monomethyl ether (boiling point 187°C), dipropylene glycol monobutyl ether (boiling point 231°C), tripropylene glycol monomethyl ether (boiling point 247°C), di ... Preferred examples of high-boiling solvents that can be used include dimethyl ether (boiling point 242°C), γ-butyrolactone (boiling point 204°C), benzyl alcohol (boiling point 205°C), propylene carbonate (boiling point 242°C), tetraethylene glycol dimethyl ether (boiling point 275°C), 1,6-diacetoxyhexane (boiling point 260°C), dipropylene glycol (boiling point 230°C), 1,3-butylene glycol diacetate (boiling point 232°C), and various other high-boiling solvents described in paragraphs 0023 to 0031 of the publication.

[0124] As a solvent having a boiling point of less than 160° C., for example, cyclohexanone (boiling point 156° C.) can be preferably used.

[0125] The content of the solvent (B) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.

[0126] <Acid, Salt Thereof, and Acid Generator> The composition for forming a resist underlayer film, which is one embodiment of the present invention, may contain an acid and / or a salt thereof and / or an acid generator.

[0127] Examples of the acid include 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 naphthalenecarboxylic acid.

[0128] The salt may be a salt of the above-mentioned acid, and is not limited thereto, but suitable salts include ammonia derivative salts such as trimethylamine salts and triethylamine salts, pyridine derivative salts, and morpholine derivative salts.

[0129] The acid and / or salt thereof may be used singly or in combination of two or more kinds, and the blending amount is usually 0.0001 to 20 mass %, preferably 0.0005 to 10 mass %, and more preferably 0.01 to 5 mass %, based on the total solid content.

[0130] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0131] Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0132] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the underlayer film to be adjusted. This is one way to match the acidity of the underlayer film to that of the upper layer resist. Adjusting the acidity of the underlayer film also allows for adjustment of the pattern shape of the upper layer resist.

[0133] Examples of the photoacid generator contained in the composition for forming a resist underlayer film of the present invention include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0134] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0135] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0136] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0137] The acid generators may be used singly or in combination of two or more.

[0138] When an acid generator is used, the proportion thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, relative to 100 parts by mass of the solid content of the composition for forming a resist underlayer film.

[0139] The composition for forming a resist underlayer film, which is one embodiment of the present invention, may contain, in addition to the above, a crosslinking agent, a surfactant, a light absorbing agent, a rheology adjuster, an adhesion aid, and the like, as necessary.

[0140] <Crosslinking Agent> Typical examples of the crosslinking agent include aminoplast crosslinking agents and phenoplast crosslinking agents.

[0141] As the crosslinking agent, a crosslinking agent having high heat resistance can be used, and as the crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0142] Aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, and polymers thereof. Preferred are crosslinking agents having at least two crosslink-forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds can also be used.

[0143] Preferably, it is at least one selected from the group consisting of tetramethoxymethyl glycoluril and hexamethoxymethyl melamine.

[0144] Some specific examples are as follows:

[0145]

[0146] Phenoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatics, their polymers, and the like. Preferred crosslinking agents have at least two crosslink-forming substituents per molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0147] In addition to the above, other examples of such compounds include compounds having a partial structure of the following formula (4) and polymers or oligomers having a repeating unit of the following formula (5).

[0148] The above R １１ , R １２ , R １３ , and R １４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the above-mentioned examples of these alkyl groups can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. Oligomers and polymers having a repeating unit structure number of 2 to 100 or 2 to 50 can be used.

[0149] Some specific examples are as follows:

[0150]

[0151]

[0152]

[0153]

[0154] The crosslinking agents, such as aminoplast crosslinking agents and phenoplast crosslinking agents, may be used alone or in combination of two or more. The aminoplast crosslinking agent may be produced by a known method or a method equivalent thereto, or a commercially available product may be used.

[0155] The amount of the crosslinking agent, such as an aminoplast crosslinking agent or a phenoplast crosslinking agent, used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, and the like, but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more, and is 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less, relative to the total solids content of the composition for forming a resist underlayer film of the present invention.

[0156] The composition for forming a resist underlayer film according to the present invention can contain a surfactant in order to prevent pinholes, striations, etc., and to further improve the coatability for preventing surface irregularities.

[0157] <Surfactant> Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Examples of suitable surfactants include fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-40 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0158] The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film of the present invention. These surfactants may be added alone or in combination of two or more.

[0159] Examples of the light absorber include commercially available light absorbers described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as C.I. 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; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; C.I. C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C.I. Fluorescent Brightening Agent 112, 135, and 163; C.I. Solvent Orange 2 and 45; C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, and 49; C.I. Pigment Green 10; C.I. Pigment Brown 2, etc. can be suitably used. The light-absorbing agent is usually blended in an amount of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the composition for forming a resist underlayer film according to the present invention.

[0160] The rheology modifier is added primarily to improve the fluidity of the resist underlayer film-forming composition, thereby improving the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes, particularly during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl 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; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0161] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the composition for forming a resist underlayer film, and particularly to prevent peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion promoter include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion promoters are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the composition for forming a resist underlayer film according to the present invention.

[0162] The solids content of the composition for forming a resist underlayer film according to the present invention is 0.1 to 70% by mass, or 0.1 to 60% by mass. The solids content is the content of all components excluding the solvent from the composition for forming a resist underlayer film. The solids content may contain a crosslinkable resin in an amount of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0163] (Resist Underlayer Film) The resist underlayer film can be formed, for example, as follows using the composition for forming a resist underlayer film according to the present invention.

[0164] Substrates used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon dioxide coated substrates (SiO ２ The resist underlayer film-forming composition according to one embodiment of the present invention is applied onto a substrate (e.g., 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, or low-dielectric-constant material (low-k material)-coated substrate) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to form a coated film. Baking conditions are appropriately selected from a baking temperature of 80°C to 800°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 500°C and the baking time is 0.5 to 2 minutes. The atmospheric gas during baking may be air, or an inert gas such as nitrogen or argon. In one embodiment, an oxygen concentration of 1% or less is particularly preferred. The thickness of the underlayer film formed here 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 imprint mold (mold replica) can be produced.

[0165] (Plasma Treatment) Subsequently, the coating film is subjected to a plasma treatment to obtain the resist underlayer film of the present invention. The plasma treatment conditions, for example, include a source power of preferably 0 to 20,000 W, more preferably 1 to 20,000 W, and even more preferably 1 to 5,000 W. The bias voltage (bias power) is preferably 0 to 20,000 V, more preferably 1 to 20,000 V, and even more preferably 1 to 5,000 V. The pressure is preferably 0 to 20,000 mTorr, and more preferably 0 to 10,000 mTorr. The gas supply flow rate is preferably 1 to 5,000 sccm. The temperature is preferably −100 to 600° C., and more preferably −10 to 300° C. The treatment time is preferably 1 to 1,200 seconds.

[0166] The range in which the film properties such as etching resistance are changed by the plasma treatment can be, for example, the surface of the underlayer film, or from the surface to 1 nm, or from the surface to 5 nm, or from the surface to 20 nm, or from the surface to the bottom, based on the film after the plasma treatment. The film properties of the underlayer film can be changed continuously in the film thickness direction.

[0167] The etching resistance of the resist underlayer film of the present invention is improved by subjecting it to plasma treatment. The etching resistance of the resist underlayer film after plasma treatment relative to the etching resistance of the resist underlayer film (coating film) before plasma treatment is preferably 1.01 times or more, more preferably 1.05 times or more, and even more preferably 1.10 times or more. The upper limit of the etching resistance of the resist underlayer film after plasma treatment relative to the etching resistance of the resist underlayer film (coating film) before plasma treatment is not particularly limited, but is, for example, 5.0 times. The etching resistance of the resist underlayer film before and after plasma treatment can be determined, for example, by the method described in the Examples.

[0168] The gas used in the plasma treatment preferably contains at least a rare gas, nitrogen, and hydrogen, and examples of the rare gas include helium, neon, and argon.

[0169] The method for producing a resist underlayer film according to one embodiment of the present invention preferably further comprises, after the plasma treatment, a step of baking the semiconductor substrate on which the resist underlayer film has been formed at 200 to 500° C. Air may be used as the atmospheric gas during the baking, or an inert gas such as nitrogen or argon may also be used.

[0170] (Ion Implantation Treatment) The resist underlayer film of the present invention can also be obtained by subjecting the coating film to ion implantation treatment instead of plasma treatment. The ion implantation treatment can be performed using, for example, an ion implantation apparatus. The ion implantation apparatus includes, for example, a high-voltage unit, a transport unit, and a process chamber. The high-voltage unit includes an ion generation source, an ion extraction unit, a mass analysis unit, and a slit. The ion generation source generates ions to be implanted. The ion extraction unit extracts ions generated from the ion generation source. The mass analysis unit uses a magnetic field to bend the direction of ion travel. The ions then pass through the slit, extracting desired ions. The transport unit includes an acceleration unit and a scanning unit. The acceleration unit accelerates ions that have passed through the slit. The scanning unit scans the accelerated ion beam. The ion implantation target is placed in the process chamber. The ion beam scanned by the ion beam scanning unit is irradiated onto the ion implantation target. In this way, the ion implantation apparatus implants ions into the ion implantation target (coating film). The ions to be implanted include, for example, C, Ar, Xe, He, Ne, and N. ２ , Kr, CO ２ , H ２ , O ２ , B.F. ３ , P.H. ３ , AsH ３ , SiF ４ , BCL ３ , P.F. ３ , GeH ４ , B ２ H ６ etc.

[0171] When C (carbon) is ion-implanted, the implantation energy is, for example, 1 to 20 keV, and the implantation amount is, for example, 1×10 １４ ~5 x 10 １４ [atoms / cm ２ In addition, when ion implanting Ar (argon), the implantation energy is, for example, 1 to 100 keV, and the implantation amount is, for example, 5×10 １４ ~5 x 10 １６ [atoms / cm ２In addition, when Xe (xenon) ions are implanted, the implantation energy is, for example, 1 to 200 [keV], and the implantation amount is, for example, 1×10 １４ ~5 x 10 １５ [atoms / cm ２ ] range can be used.

[0172] The change in film thickness of the underlayer film due to the ion implantation treatment is, for example, 100 to 50%, or 95 to 60%, or 90 to 70% of the film thickness before the treatment, where the film thickness before the treatment is taken as 100%. The range in which the film physical properties such as etching resistance change due to the ion implantation treatment can be, for example, the surface of the underlayer film, or from the surface to 1 nm, or from the surface to 5 nm, or from the surface to 20 nm, or from the surface to the bottom, based on the film after the ion implantation treatment. The film physical properties of the underlayer film can be continuously changed in the film thickness direction.

[0173] The resist underlayer film of the present invention has improved etching resistance due to ion implantation. The etching resistance of the resist underlayer film after ion implantation is preferably 1.01 times or more, more preferably 1.05 times or more, and even more preferably 1.10 times or more relative to the etching resistance of the resist underlayer film before ion implantation. The upper limit of the etching resistance of the resist underlayer film after ion implantation relative to the etching resistance of the resist underlayer film before ion implantation is not particularly limited, but is, for example, 5.0 times. The etching resistance of the resist underlayer film before and after ion implantation can be determined, for example, by the same method as that for the etching resistance of the resist underlayer film before and after plasma treatment.

[0174] The gas used in the ion implantation process preferably contains at least a rare gas, nitrogen, and hydrogen, and examples of the rare gas include helium, neon, and argon.

[0175] The method for producing a resist underlayer film according to one embodiment of the present invention preferably further comprises, after the ion implantation treatment, a step of baking the semiconductor substrate on which the resist underlayer film has been formed at 200 to 500° C. Air may be used as the atmospheric gas during baking, or an inert gas such as nitrogen or argon may also be used.

[0176] Next, an adhesion layer and / or a silicon-containing layer containing 99% by mass or less, or 50% by mass or less of Si can be formed on the resist underlayer film according to one embodiment of the present invention by coating or vapor deposition. For example, an adhesion layer as described in JP-A-2013-202982 or JP-A-5827180, a silicon-containing resist underlayer film (inorganic resist underlayer film) forming composition as described in WO 2009 / 104552 (A1) can be formed by spin coating, or a Si-based inorganic material film can be formed by CVD or the like.

[0177] Furthermore, by applying the composition for forming a resist underlayer film, which is one embodiment of the present invention, to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, the step between the portion with a step and the portion without a step can be reduced.

[0178] (Method of forming a resist pattern) A method of forming a resist pattern according to one embodiment of the present invention includes the steps of forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film according to one embodiment of the present invention, and forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment. The method of forming a resist pattern according to one embodiment of the present invention is used in the manufacture of semiconductors.

[0179] (Method for manufacturing a semiconductor device) (i) A method for manufacturing a semiconductor device, which is one aspect of the present invention, includes the steps of: forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film, which is one aspect of the present invention; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam and developing it to form a resist pattern; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[0180] (ii) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a coating film on a semiconductor substrate using the resist underlayer film-forming composition according to one aspect of the present invention; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing the semiconductor substrate through the patterned resist underlayer film.

[0181] (iii) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a coating film on a semiconductor substrate using the resist underlayer film-forming composition according to one aspect of the present invention; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing the semiconductor substrate through the patterned resist underlayer film.

[0182] (iv) A method for manufacturing a semiconductor device according to one embodiment of the present invention includes the steps of: forming a coating film on a semiconductor substrate using the resist underlayer film-forming composition according to one embodiment of the present invention; forming a resist underlayer film by subjecting the coating film to a plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after removing the hard mask; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer), and processing the semiconductor substrate through the patterned vapor-deposited film (spacer).

[0183] The manufacturing methods (i) to (iv) above can be used to process a semiconductor substrate.

[0184] The step of forming a resist underlayer film using the composition for forming a resist underlayer film, which is one embodiment of the present invention, is as described above in (Resist underlayer film).

[0185] A hard mask such as a silicon-containing film may be formed as a second resist underlayer film on the resist underlayer film formed in the above steps, and a resist pattern may be formed thereon [(ii) to (iv) above].

[0186] The hard mask may be a coating film of an inorganic material or a vapor-deposited film of an inorganic material formed by a vapor deposition method such as CVD or PVD, and may be a SiON film, a SiN film, or a SiO ２ An example is a membrane.

[0187] Furthermore, an anti-reflective coating (BARC) may be formed on this hard mask, or a resist shape correction film without anti-reflective properties may be formed.

[0188] In the step of forming the resist pattern, exposure is performed through a mask (reticle) for forming a predetermined pattern or by direct writing. Examples of exposure sources that can be used include g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and electron beam. After exposure, post-exposure baking is performed as needed. The resist is then developed with a developer (e.g., a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, butyl acetate), and then rinsed with a rinse solution or pure water to remove the used developer. Post-baking is then performed to dry the resist pattern and enhance adhesion to the underlayer.

[0189] The etching step performed after the formation of the resist pattern is performed by dry etching.

[0190] The following gases are used for processing the hard mask (silicon-containing layer), resist underlayer film, and substrate: CF ４ , CHF ３ , C.H. ２ F ２ , CH ３ F, C ４ F ６ , C ４ F ８ , O ２ , N ２ O, NO ２ , H ２ , He can be used. These gases may be used alone or in combination of two or more. Furthermore, these gases may be mixed with argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride.

[0191] The resist film may be patterned by a nanoimprint method or a self-assembled film method.

[0192] In the nanoimprint method, a resist composition is molded using a patterned mold that is transparent to irradiated light, while in the self-assembled film method, a pattern is formed using a self-assembled film that naturally forms a regular structure on the nanometer order, such as a diblock polymer (e.g., polystyrene-polymethyl methacrylate).

[0193] In the nanoimprint method, before applying the curable composition that will form the resist film, a silicon-containing layer (hard mask layer) may be optionally formed on the resist underlayer film by coating or vapor deposition, and further an adhesion layer may be formed on the resist underlayer film or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that will form the resist film may be applied on the adhesion layer.

[0194] In addition, wet etching may be performed to simplify the process and reduce damage to the processed substrate. This leads to suppression of fluctuations in processing dimensions and reduction of pattern roughness, making it possible to process the substrate with high yield. Therefore, in steps (iii) to (iv), the hard mask can be removed using either etching or an alkaline chemical solution. In particular, when an alkaline chemical solution is used, there are no restrictions on the components, but it is preferable that the alkaline component contains the following:

[0195] Examples of the alkaline component include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, and (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N , N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, 1,5-diazabicyclo[4.3.0]nonene-5, etc. Furthermore, particularly from the viewpoint of handling, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base may be used in combination with the quaternary ammonium hydroxide. As the inorganic base, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, rubidium hydroxide, etc. are preferred, with potassium hydroxide being more preferred.

[0196] Next, the present invention will be explained in detail with reference to synthesis examples and examples, but the present invention is not limited to these.

[0197] The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 5 below were measured by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions were as follows: Column temperature: 40°C, Flow rate: 0.35 ml / min, Eluent: tetrahydrofuran (THF), Standard sample: polystyrene (Tosoh Corporation).

[0198] Synthesis of Resins Resins (S1) to (S6) used in the resist underlayer films were synthesized using the following compound group A, catalyst group B, and solvent group C. Compounds A1, A5, A8, and A11 were purchased products. A1: VP-8000 manufactured by Nippon Soda Co., Ltd. A5: YX-4000 manufactured by Mitsubishi Chemical Corporation A8: EHPE-3150 manufactured by Daicel Corporation A11: NC-7300L manufactured by Nippon Kayaku Co., Ltd.

[0199] ○Compound group A

[0200] Catalyst group B Azobisisobutyronitrile: B1 Tetrabutylphosphonium bromide: B2 Ethyltriphenylphosphonium bromide: B3

[0201] Solvent group C: Propylene glycol monomethyl ether acetate (=PGMEA): C1 Propylene glycol monomethyl ether (=PGME): C2

[0202] [Synthesis Examples 1 to 5] The compounds, catalysts, and solvents listed in Table 1 below were placed in a flask, and after replacing the atmosphere in the flask with nitrogen, a reaction was carried out for a predetermined time and at a predetermined temperature. After the reaction was stopped, ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin as needed. Note that resin S1 is a purchased product and is therefore excluded from Table 1-1. In Table 1, the values ​​in the "Compound," "Catalyst," and "Solvent" columns represent the mass (g) of each compound, and the values ​​in the "Temperature / Time" column represent the temperature (°C) during the reaction and the reaction time (hours).

[0203]

[0204] The structural formulas and weight average molecular weights Mw of resins S1 to S6 are shown below. In the formulas, n represents the number of repeating units, and numbers such as "55" represent the proportion (molar ratio) of repeating units in the resin.

[0205]

[0206] Preparation of Resist Underlayer Films Resins (S1) to (S6), crosslinker (CL1), acid generator (Ad1), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)), and a surfactant, Megafac R-40 (manufactured by DIC Corporation, H1), were mixed in the proportions shown in Table 2 below, and the mixture was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare compositions for forming resist underlayer films (M1 to M7). The values ​​shown in Table 2 represent the parts by mass of the crosslinker, acid generator, and surfactant relative to 100 parts by mass of the resin, and the solvents represent the mass % of each solvent relative to 100% by mass of the total solvent, independent of the mass of the resin. In Table 2, "-" indicates that the component is not contained.

[0207] The structural formulae of the crosslinking agent (CL1) and the acid generator (Ad1) are shown below.

[0208]

[0209]

[0210] [Preparation of Plasma-Treated Wafers] [Examples 1 to 7, Comparative Examples 1 to 7] The resist underlayer film-forming compositions M1 to M7 were applied to silicon wafers using a coating and developing apparatus manufactured by Tokyo Electron, and baked at the predetermined temperature for the predetermined time shown in Table 3 to form resist underlayer films with a film thickness of approximately 45 nm. Thereafter, plasma treatment was performed by bombardment using He for 10 seconds using an etching apparatus manufactured by Tokyo Electron. Wafers that were not subjected to the above-described plasma treatment were also prepared as Comparative Examples 1 to 7.

[0211] [Elution test in resist solvent] The resist underlayer films (Examples 1 to 7, Comparative Examples 1 to 7) before and after plasma treatment were immersed in a PGME / PGMEA mixed solution (mass ratio = 7 / 3), a general-purpose thinner, for 60 seconds, spin-dried, and baked at 100°C for 30 seconds. The film thickness before and after immersion in the thinner was compared to confirm resistance to the solvent. A film thickness reduction of 1% or less after immersion in the thinner was evaluated as "Good", and a film thickness reduction of more than 1% was evaluated as "Poor". The results are shown in Table 3.

[0212] [Etching Rate Measurement] The resist underlayer films (Examples 1 to 7, Comparative Examples 1 to 7) were etched under the following conditions before and after plasma treatment. The film thickness was calculated using a cross-sectional SEM, and the etching resistance was evaluated from the remaining film amount. A case in which the etching rate was slower than before plasma treatment (a case in which the etching resistance was higher) was judged as "Good." The values ​​in the "Change in Etching Resistance" column were calculated as follows: An etching rate of X nm / min was calculated from the remaining film amount after etching. This was calculated for the sample with and without plasma treatment, and the value calculated using the following formula was used as the "change in etching resistance." "Change in Etching Resistance" = (Etching Rate Without Plasma Treatment) / (Etching Rate With Plasma Treatment) The results are shown in Table 3. In Table 3, an "x" in the "Etching Resistance" column indicates that no plasma treatment was performed, and therefore the etching rate is that of the resist underlayer film after baking at the specified temperature for the specified time listed in Table 1. Furthermore, a "-" in the "Change in Etching Resistance" column indicates that no plasma treatment was performed, and therefore no change in etching resistance was observed. <Etching conditions> Plasma treatment gas: octafluorocyclobutane (C ４ F ８ ), oxygen (O ２ ), Argon (Ar) Treatment time: 40 seconds

[0213]

[0214] As described above, resins having aromatic hydrocarbon rings in the molecule (either in the main chain, side chain, or both the main chain and side chain) can be significantly improved in etching resistance by plasma treatment. This property is not impaired by the addition of a crosslinker or acid generator. Furthermore, plasma treatment ensures solvent resistance without the addition of additives such as crosslinkers, eliminating the need for mixing with the material to be applied as an upper layer. Furthermore, the above resins have a lower glass transition temperature than conventional novolac resin-type organic films, resulting in improved planarization and embedding properties. Generally, there is a trade-off between planarization and improved etching resistance due to high carbon content. However, the resins of the present invention overcome this trade-off, making them suitable for a wide range of advanced semiconductor processes with increasingly sophisticated requirements. Similar effects to plasma treatment can also be achieved by ion implantation.

Claims

1. A composition for forming a resist underlayer film that can form a resist underlayer film that can be enhanced in etching resistance by plasma treatment or ion implantation treatment, the composition for forming a resist underlayer film comprising a resin (A) having an aromatic hydrocarbon ring and a solvent (B), wherein the resin (A) is at least one of a vinyl resin, a polyester resin, a polyether resin, a resin having an ether bond or an ester bond in the side chain, a polyimide resin, and a polyamide resin.

2. The composition for forming a resist underlayer film according to claim 1, wherein the resin (A) comprises the vinyl resin, and the vinyl resin comprises a resin having at least a structural unit represented by the following formula (A-1): (In formula (A-1), R １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms; X ０ represents a single bond, —COO—, or —CONH—; L ０ represents a monovalent organic group having an aromatic hydrocarbon ring.

3. The composition for forming a resist underlayer film according to claim 1, wherein the resin (A) comprises the polyester-based resin or the polyether-based resin, and the polyester-based resin and the polyether-based resin comprise at least one of a resin having a structural unit represented by the following formula (A-2) and a resin having a structural unit represented by the following formula (A-3): (In formula (A-2), each A independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ and Q ２ each independently represents a divalent organic group; １ and Q ２ Both or either one of X has an aromatic hydrocarbon ring; １ ~X ４ each independently represents a single bond, an ether bond, or an ester bond. (In formula (A-3), T ３ represents a group having a monocyclic aliphatic ring constituting the main chain, and Q ３ represents a divalent linking group, Ar ３ represents an aromatic hydrocarbon ring which may have a substituent.

4. The composition for forming a resist underlayer film according to claim 1, wherein the resin (A) comprises a resin having an ether bond or an ester bond in the side chain, and the resin having an ether bond or an ester bond in the side chain comprises a resin having at least a structural unit represented by the following formula (A-4): (In formula (A-4), Ar ４ represents an optionally substituted benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring; L ５ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxy group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether bond-containing group, and m5 represents an integer of 0 to 5. When m5 is 2 to 5, multiple L ５ may be the same or different. ４ represents a divalent organic group constituting the main chain, and Q ４ represents a divalent linking group having an ether bond or an ester bond, and Q ５ represents a monovalent organic group which may have a substituent; and k represents an integer of 1 to 3.

5. The composition for forming a resist underlayer film according to claim 1, wherein the solvent (B) comprises at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.

6. The composition for forming a resist underlayer film according to claim 1, further comprising at least one member selected from the group consisting of an acid, a salt thereof, and an acid generator.

7. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent.

8. The composition for forming a resist underlayer film according to claim 1, further comprising a surfactant.

9. The composition for forming a resist underlayer film according to claim 1, wherein the etching resistance of the resist underlayer film after the plasma treatment is 1.01 times or more higher than the etching resistance of the resist underlayer film before the plasma treatment.

10. The composition for forming a resist underlayer film according to claim 1, wherein the etching resistance of the resist underlayer film after ion implantation is at least 1.01 times that of the resist underlayer film before ion implantation.

11. A method for producing a resist underlayer film, comprising the steps of forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 10, and subjecting the coating film to a plasma treatment or ion implantation treatment to form a resist underlayer film.

12. A method for forming a resist pattern used in the manufacture of semiconductors, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 10; and forming a resist underlayer film by subjecting the coating film to plasma treatment or ion implantation treatment.

13. A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 10; forming a resist underlayer film by subjecting the coating film to plasma treatment or ion implantation treatment; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

14. A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 10; forming a resist underlayer film by subjecting the coating film to plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

15. A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 10; forming a resist underlayer film by subjecting the coating film to plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing a semiconductor substrate through the patterned resist underlayer film.

16. A method for manufacturing a semiconductor device, comprising: forming a coating film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 10; forming a resist underlayer film by subjecting the coating film to plasma treatment or ion implantation treatment; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film on the resist underlayer film after removing the hard mask; processing the vapor-deposited film by etching; removing the patterned resist underlayer film to leave a patterned vapor-deposited film; and processing a semiconductor substrate through the patterned vapor-deposited film.

17. The method for manufacturing a semiconductor device according to claim 14, wherein the hard mask is formed by applying a composition containing an inorganic substance or by vapor deposition of an inorganic substance.

18. The method for manufacturing a semiconductor device according to claim 13, wherein the resist film is patterned by a nanoimprint method or a self-assembled film.

19. The method for manufacturing a semiconductor device according to claim 15, wherein the hard mask is removed by either etching or an alkaline chemical solution.

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