Resist underlayer film-forming composition

Abstract

This resist underlayer film-forming composition is for use in electron beam lithography or EUV lithography, and contains a solvent and a polymer having a structural unit represented by formula (1). (In formula (1), each A independently represents a hydrogen atom, a methyl group, or an ethyl group. Q represents a divalent group. X represents a hydrogen atom or a nitro group.)

Description

Composition for forming resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for producing a semiconductor element, and a method for forming a 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 then 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 other factors 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] As a composition for forming a resist underlayer film, an anti-reflective coating-forming composition containing a polymer having a structure represented by formula (1) and a solvent has been proposed (see Patent Document 1; for formula (1), see claim 1 of Patent Document 1).

[0004] International Publication No. 2005 / 098542

[0005]

[0006] Properties required for a resist underlayer film include, for example, no intermixing with a resist film formed on an overlying layer (being insoluble in a resist solvent), and the ability to form a good resist pattern with reduced resist pattern variation. In particular, resist pattern variation in ultrafine lithography such as electron beam lithography and EUV lithography significantly affects the performance of the semiconductor device manufactured. The present invention has been made in view of the above circumstances, and aims to provide a composition for forming a resist underlayer film that can form a good resist pattern with reduced resist pattern variation, as well as a method for manufacturing a resist underlayer film, a laminate, and a semiconductor device, and a pattern formation method using the resist underlayer film composition.

[0006] 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.

[0007] That is, the present invention includes the following aspects: [1] A composition for forming a resist underlayer film used in electron beam lithography or EUV lithography, the composition for forming a resist underlayer film comprising a polymer having a structural unit represented by the following formula (1), and a solvent: (In formula (1), each A independently represents a hydrogen atom, a methyl group, or an ethyl group. Q represents a divalent group. X represents a hydrogen atom or a nitro group.) [2] The composition for forming a resist underlayer film according to [1], wherein Q in formula (1) is represented by the following formula (1-1) or formula (1-2): (In formula (1-1), Q １ represents a divalent organic group having 1 to 30 carbon atoms. n1 and n2 each independently represent 0 or 1. In formula (1-2), X １ represents a group represented by any one of the following formulas (1-2-1) to (1-2-3). １ and Z ２ each independently represents a single bond or a group represented by the following formula (1-2-4). * represents a bond. (In formulas (1-2-1) to (1-2-3), R１ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy 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 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom in formula (1-2). *2 represents a bond bonding to a nitrogen atom in formula (1-2). (In formula (1-2-4), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (1-2). *4 represents a bond.) [3] The composition for forming a resist underlayer film according to [1] or [2], wherein the polymer has a structure represented by the following formula (E) at a terminal thereof: (In formula (E), E represents a group having 1 to 20 carbon atoms, n represents 0 or 1, and * represents a bond.) [4] The composition for forming a resist underlayer film according to [3], wherein E in formula (E) represents a monovalent group having a ring structure. [5] The composition for forming a resist underlayer film according to any one of [1] to [4], wherein the polymer has an ester bond concentration of 0.030 g to 0.340 g per 1 g of the polymer. [6] The composition for forming a resist underlayer film according to any one of [1] to [5], wherein the solvent contains at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers. [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 [7], wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. [9] The composition for forming a resist underlayer film according to any one of [1] to [8], further comprising a curing catalyst.

[10] A resist underlayer film, which is a cured product of the composition for forming a resist underlayer film according to any one of [1] to [9].

[11] A laminate comprising: a semiconductor substrate; and the resist underlayer film according to

[10] .

[12] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [9]; and forming a resist film on the resist underlayer film.

[13] A method for forming a pattern, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [9]; forming a resist film on the resist underlayer film; irradiating the resist film with an electron beam or EUV, and then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a composition for forming a resist underlayer film that can form a good resist pattern while suppressing variation in the resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor element, and a pattern forming method, all of which use the composition for forming a resist underlayer film.

[0009] (Composition for forming a resist underlayer film) The composition for forming a resist underlayer film of the present invention contains a polymer having a structural unit represented by the following formula (1), and a solvent. The composition for forming a resist underlayer film may also contain a crosslinking agent, a curing catalyst, etc. The composition for forming a resist underlayer film is used in electron beam lithography or EUV lithography. EUV is extreme ultraviolet light with a wavelength of 13.5 nm.

[0010] When the composition for forming a resist underlayer film contains a polymer having a structural unit represented by the following formula (1), a resist pattern with reduced variation can be formed on the resist underlayer film formed from the composition for forming a resist underlayer film.

[0011] <Polymer> The polymer has a structural unit represented by the following formula (1): The polymer may further have a structural unit other than the structural unit represented by the following formula (1). (In formula (1), each A independently represents a hydrogen atom, a methyl group, or an ethyl group. Q represents a divalent group. X represents a hydrogen atom or a nitro group.)

[0012] In formula (1), the bonding positions of the two ester bonds to the benzene ring are not particularly limited and may be any of the o-position, m-position, and p-position. However, from the viewpoint of suitably obtaining the effects of the present invention, the m-position and p-position are preferred.

[0013] In formula (1), X represents a hydrogen atom or a nitro group. From the viewpoint of suitably achieving the effects of the present invention, X is preferably a nitro group. When X represents a nitro group, the bonding positions of the two ester bonds to the benzene ring are preferably the 3rd and 5th positions, assuming that X is the 1st position.

[0014] Q in formula (1) is not particularly limited as long as it is a divalent group. The number of carbon atoms in the divalent group may be, for example, 1 to 40, 1 to 20, or 1 to 15.

[0015] Q in formula (1) may or may not have a ring structure. Q in formula (1) may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms. Q in formula (1) may have a halogen atom. In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] From the viewpoint of suitably obtaining the effects of the present invention, Q in formula (1) is preferably represented by the following formula (1-1) or formula (1-2). (In formula (1-1), Q １ represents a divalent organic group having 1 to 30 carbon atoms. n1 and n2 each independently represent 0 or 1. In formula (1-2), X １ represents a group represented by any one of the following formulas (1-2-1) to (1-2-3). １ and Z ２ each independently represents a single bond or a group represented by the following formula (1-2-4). * represents a bond. (In formulas (1-2-1) to (1-2-3), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy 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 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom in formula (1-2). *2 represents a bond bonding to a nitrogen atom in formula (1-2). (In formula (1-2-4), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (1-2). *4 represents a bond.)

[0017] Q in formula (1-1) １ represents a divalent organic group having 1 to 30 carbon atoms. １ The number of carbon atoms in may be 1 to 25, or may be 1 to 20. １ may or may not have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings. １ represents, for example, an alkylene group, a phenylene group, a naphthylene group, an anthrylene group, a group represented by the following formula (1-1-1), or a group represented by the following formula (1-1-2), and the phenylene group, the naphthylene group, and the anthrylene group may each independently be substituted with a group or atom selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. (In formulas (1-1-1) and (1-1-2), R ａ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. W represents a single bond, —CH ２-, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -CO-, -O-, -S- or SO ２ Each m independently represents 0 or 1. Each n independently represents an integer of 0 to 4.

[0018] Q in formula (1-1) １ The alkylene group in formula (1-1) may be, for example, an alkylene group having 1 to 15 carbon atoms. The alkylene group may have a ring structure. Examples of the ring structure include a cyclohexane ring. １ When is an alkylene group, examples of the group represented by formula (1-1) include the following groups. (* represents a bond.)

[0019] Q in formula (1-1) １ When has a phenylene group or a naphthylene group, examples of the group represented by formula (1-1) include the following groups. (* represents a bond.)

[0020] Q in formula (1-1) １ When is formula (1-1-1) or formula (1-1-2), examples of the group represented by formula (1-1) include the following groups. (* represents a bond.)

[0021] Examples of the group represented by formula (1-2) include the following groups. (* represents a bond.)

[0022] The polymer may further have a structure represented by the following formula (E) at its terminal: The structure represented by formula (E) may be present at one terminal or both terminals of the polymer. (In formula (E), E represents a group having 1 to 20 carbon atoms, n represents 0 or 1, and * represents a bond.)

[0023] E in formula (E) is not particularly limited as long as it is a group having 1 to 20 carbon atoms. E in formula (E) represents, for example, a monovalent group having a ring structure. Examples of the ring structure include an aromatic ring and a non-aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. The non-aromatic ring may be, for example, a monocyclic ring or a polycyclic ring. Furthermore, the non-aromatic ring may be a hydrocarbon ring or a heterocyclic ring. A polycyclic non-aromatic ring may be a hydrocarbon ring or a fused ring of a hydrocarbon ring and a heterocyclic ring. E in formula (E) may or may not have a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. E in formula (E) may or may not have a halogen atom.

[0024] Examples of the structure represented by formula (E) include structures represented by the following formulas (E-1) to (E-10). (In formula (E-1), R Ｅ１ , R Ｅ２ and R Ｅ３ each independently represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 13 carbon atoms, a nitro group, or a hydroxy group, and n represents 0 or 1. * represents a bond.

[0025] (In formulas (E-2) to (E-4), R Ｅ４ represents a hydrogen atom or a methyl group, R Ｅ５ and R Ｅ６ each independently represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group, a phenyl group, a benzyl group, a benzyloxy group, a benzylthio group, an imidazole group, or an indole group, and the hydrocarbon group, the alicyclic hydrocarbon group, the phenyl group, the benzyl group, the benzyloxy group, the benzylthio group, the imidazole group, or the indole group may have at least one hydroxy group or methylthio group as a substituent; RＥ７ represents a hydrogen atom or a hydroxy group, and Q Ｅ１ represents an arylene group, each n independently represents 0 or 1, y represents an integer of 1 to 4, w represents an integer of 1 to 4, x1 represents 0 or 1, and x2 represents an integer of 1 to 5. * represents a bond.

[0026] (In formula (E-5), R Ｅ８ , R Ｅ９ and R Ｅ１０ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 13 carbon atoms, a halogen atom, a nitro group, or a hydroxy group, and Ｅ８ , R Ｅ９ and R Ｅ１０ at least one of represents the alkyl group, Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and the two carbonyl groups are bonded to two adjacent carbon atoms of the ring represented by Ar, Ｅ１ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have an alkoxy group having 1 to 3 carbon atoms as a substituent. * represents a bond.

[0027] (In formula (E-6) and formula (E-7), R Ｅ１１ represents an alkyl group having 1 to 6 carbon atoms, which may have a substituent, a phenyl group, a pyridyl group, a halogen atom, or a hydroxy group; R Ｅ１２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogen atom, or an ester group represented by -C(=O)O-X, where X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R Ｅ１３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a halogen atom; R Ｅ１４ represents a single bond or a divalent organic group having 1 to 8 carbon atoms; R Ｅ１５ represents a divalent organic group having 1 to 8 carbon atoms; A Ｅ１ each independently represents an aromatic ring or an aromatic heterocycle, each n independently represents 0 or 1, and u represents 1 or 2. * represents a bond.

[0028] (In formula (E-8) and formula (E-9), A Ｅ２ each independently represents an aryl group having 6 to 40 carbon atoms; R Ｅ１６ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R Ｅ１７ and R Ｅ１８ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 40 carbon atoms; n represents 0 or 1; n1 and n3 each independently represent an integer of 1 to 12; n2 represents an integer of 0 to 11; * represents a bond.

[0029] (In formula (E-10), X represents a phenyl group, a naphthyl group, or an anthracenyl group substituted with at least one group selected from the group consisting of a halogen atom, a hydroxy group, and a linear or branched alkoxy group having 1 to 6 carbon atoms; n represents 0 or 1; and * represents a bond.)

[0030] Specific examples of E in formula (E) include the following groups. (* represents a bond.)

[0031] If the ester bond concentration in the polymer is too high or too low, the effects of the present invention will not be favorably exhibited. In this regard, the ester bond concentration in the polymer is preferably 0.030 g to 0.340 g per 1 g of polymer. For example, if a dicarboxylic acid or a dicarboxylic acid ester is not used when synthesizing the polymer, the ester bond concentration will be 0 g or will be small. For example, if a tricarboxylic acid or a tetracarboxylic acid or an ester thereof is used when synthesizing the polymer, the ester bond concentration will be large and tend to exceed 0.340 g.

[0032] The ester bond concentration can be calculated, for example, by performing a compositional analysis of the polymer and determining the proportion of ester bonds (-COO-; 44 g / mol) per 1 g of the polymer from the results. The ester bond concentration can also be calculated from the amount of ester bonds in the reaction raw materials used in synthesizing the polymer. When the polymer and the reaction raw materials have carboxy groups, the ester bonds in the carboxy groups are included in the ester bonds that are the subject of the ester bond concentration calculation.

[0033] The mass proportion of the structural unit represented by formula (1) in the polymer is not particularly limited, but is preferably 30 mass %, more preferably 50 mass %, and particularly preferably 70 mass % or more.

[0034] The method for producing the polymer is not particularly limited, and examples thereof include the following methods (i) to (iv): (i): A method of reacting a diepoxy compound represented by the following formula (1A) with a compound represented by the following formula (1-1A) or formula (1-2A); (ii): A method of reacting a diepoxy compound represented by the following formula (1A), a compound represented by the following formula (1-1A) or formula (1-2A), and a compound represented by the following formula (EA); (iii): A method of reacting a dicarboxylic acid represented by the following formula (1B) with a diepoxy compound represented by the following formula (1-1B) or formula (1-2B); (iv): A method of reacting a dicarboxylic acid represented by the following formula (1B), a diepoxy compound represented by the following formula (1-1B) or formula (1-2B), and a compound represented by the following formula (EA). Note that in (i) to (iv), other compounds may be used in combination. By using the compound represented by formula (EA), the group represented by formula (E) can be introduced into the terminal of the polymer.

[0035] (In formula (1A), A and X are the same as A and X in formula (1), respectively.)

[0036] (In formula (1-1A), Q １ , n1, and n2 are respectively Q in formula (1-1). １ , n1, and n2.)

[0037] (In formula (1-2A), X １ , Z １ , and Z ２ are X in formula (1-2), respectively. １ , Z １ , and Z ２ It is the same as Z. １ and Z ２ The hydrogen atom bonded to is usually an active hydrogen.

[0038] (In formula (1B), X represents a hydrogen atom or a nitro group.)

[0039] (In formula (1-1B), Q １ , n1, and n2 are respectively Q in formula (1-1). １ , n1, and n2 are the same as A in formula (1).

[0040] (In formula (1-2B), X １ , Z １ , and Z ２ are X in formula (1-2), respectively. １ , Z １ , and Z ２ Each A is the same as A in formula (1).

[0041] (In formula (EA), n and E are the same as n and E in formula (E), respectively.)

[0042] The weight-average molecular weight Mw of the polymer is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, and particularly preferably 2,000 to 10,000. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0043] The content of the polymer in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 100% by mass, more preferably 50% by mass to 95% by mass, and particularly preferably 60% by mass to 90% by mass, based on the film-constituting components. The film-constituting components refer to components other than the solvent in the composition for forming a resist underlayer film.

[0044] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether and monocarboxylic acid ester of alkylene glycol monoalkyl ether.

[0045] Examples of the alkylene group of the alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8. Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0046] Examples of the alkylene group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the monocarboxylic acid of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include those having 5 to 10 carbon atoms. Examples of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0047] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0048] Among these solvents, alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0049] These solvents may be used alone or in combination of two or more.

[0050] The mass proportion of the organic solvent in the solvent is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0051] The content of the solvent 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.

[0052] <Crosslinking Agent> The crosslinking agent is not particularly limited and has a structure different from that of the polymer.

[0053] Preferred crosslinking agents are aminoplast crosslinking agents and phenoplast crosslinking agents. Aminoplast crosslinking agents are addition condensation products of a compound having an amino group, such as melamine or guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensation products of a compound having a phenolic hydroxy group with formaldehyde.

[0054] Examples of the crosslinking agent include compounds having two or more of the following structures: (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0055] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0056] The crosslinking agent (C) is preferably a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group, which may be used alone or in combination of two or more.

[0057] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0058] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0059] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0060] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0061] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0062] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0063] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0064] (In formula (3d), R １ represents a methyl group or an ethyl group.

[0065] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0066] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0067] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. １ is 1≦n １ an integer ≦3, n ２ is 2≦n ２ n is an integer ≦5 ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n ５ an integer ≦3, n ６ is 1≦n ６ an integer ≦4, n ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0068] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ n is an integer ≦5１１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, examples of the m2-valent organic group include m2-valent organic groups having 1 to 15 carbon atoms.

[0069] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0070] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: Me represents a methyl group.

[0071] The above compounds are available as products from Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. Examples of such products include those available from Asahi Organic Chemicals Co., Ltd. under the trade names TMOM-BP and HMOM-TPPA.

[0072] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0073] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 1,000 or less.

[0074] The content of the crosslinking agent in the composition for forming a resist underlayer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, based on the polymer.

[0075] <Curing Catalyst> The curing catalyst contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0076] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0077] 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.

[0078] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0079] 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.

[0080] The curing catalyst may be used alone or in combination of two or more.

[0081] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass, relative to the crosslinking agent.

[0082] <Other Components> A surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface irregularities.

[0083] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more.

[0084] The solid content of the composition for forming a resist underlayer film of the present invention, that is, the content of components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.

[0085] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the composition for forming a resist underlayer film described above. The resist underlayer film can be produced, for example, by applying the composition for forming a resist underlayer film described above onto a semiconductor substrate and baking the applied composition.

[0086] Examples of semiconductor substrates onto which the resist underlayer film-forming composition can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0087] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0088] The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate by a suitable application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. A baking temperature of 120°C to 350°C and a baking time of 0.5 to 30 minutes are preferred, and a baking temperature of 150°C to 300°C and a baking time of 0.8 to 10 minutes are more preferred.

[0089] The thickness of the resist underlayer film may be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm ( 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0090] The method for measuring the film thickness of the resist underlayer film in this specification is as follows: Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Corporation) SWE (single wavelength ellipsometer) mode Arithmetic mean of 8 points (for example, measuring 8 points at 1 cm intervals in the X direction of the wafer)

[0091] (Laminate) The laminate of the present invention includes a semiconductor substrate and the resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrates described above. The resist underlayer film is disposed on the semiconductor substrate, for example.

[0092] (Method for manufacturing a semiconductor element, method for forming a pattern) The method for manufacturing a semiconductor element of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and forming a resist film on the resist underlayer film.

[0093] The pattern forming method of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, forming a resist film on the resist underlayer film, irradiating the resist film with an electron beam or EUV and then developing the resist film to obtain a resist pattern, and etching the resist underlayer film using the resist pattern as a mask.

[0094] Typically, a resist film is formed on the resist underlayer film. The film thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0095] The resist film formed on the resist underlayer film by a known method (e.g., coating and baking a resist composition) is not particularly limited as long as it is responsive to the electron beam or EUV used for irradiation. Both negative and positive photoresists can be used. In this specification, resists responsive to EB are also referred to as photoresists. Examples of photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0096] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0097] Examples of the resist composition include the following compositions.

[0098] An actinic ray-sensitive or radiation-sensitive resin composition comprising: Resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (121):

[0099] In the general formula (121), m represents an integer of 1 to 6. １ and R ２ each independently represents a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ - or -SO ３ - represents. ２ represents an alkylene group which may have a substituent or a single bond. １ represents a cyclic organic group which may have a substituent. ＋ represents a cation.

[0100] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to Periods 3 to 7 of Groups 3 to 15 of the periodic table.

[0101] A radiation-sensitive resin composition comprising: a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group; and an acid generator.

[0102] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R １ are the same or different. ２ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. ３ is a monovalent group having 1 to 20 carbon atoms containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R ４is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0103] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid labile group; and an acid generator.

[0104] [In the formula, R ２ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X １ represents a single bond, —CO—O—*, or —CO—NR ４ -*, * represents a bond to -Ar, R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxy group and a carboxy group.]

[0105] Examples of the resist film include the following.

[0106] A resist film comprising a base resin comprising a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain upon exposure:

[0107] (In formula (a1) and formula (a2), R Ａ are each independently a hydrogen atom or a methyl group. １ and R ２ are each independently a tertiary alkyl group having 4 to 6 carbon atoms. ３ are each independently a fluorine atom or a methyl group, and m is an integer of 0 to 4. １ X is a single bond, a phenylene group, or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ is a single bond, an ester bond, or an amide bond.

[0108] Examples of resist materials include the following:

[0109] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2):

[0110] (In formula (b1) and formula (b2), R Ａ is a hydrogen atom or a methyl group. １ is a single bond or an ester group. ２ is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group; and X ２ At least one hydrogen atom contained in X is substituted with a bromine atom. ３ Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. １ and Rf ２ may combine to form a carbonyl group. １ ~R ５ are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and in which some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate ester group. １ and R ２may be bonded to form a ring together with the sulfur atom to which they are attached.

[0111] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0112] (In formula (a), R Ａ is a hydrogen atom or a methyl group. １ is a hydrogen atom or an acid labile group. ２ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ X is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. ２ is -O-, -O-CH ２ - or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. However, m+u is an integer of 1 to 4.

[0113] A resist composition that generates an acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising: a base component (A) whose solubility in a developer changes due to the action of the acid; and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) comprises a fluororesin component (F1) that has a structural unit (f1) that includes a base dissociable group, and a structural unit (f2) that includes a group represented by the following general formula (f2-r-1):

[0114] [In formula (f2-r-1), Rf ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0115] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0116] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ represents a divalent aromatic cyclic group which may have a substituent. ０１ is a single bond or a divalent linking group. ２ are each independently an organic group having a fluorine atom.

[0117] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738.

[0118] A coating comprising a metal oxo-hydroxo network having organic ligands with metal carbon and / or metal carboxylate bonds.

[0119] Inorganic oxo / hydroxo-based compositions.

[0120] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures thereof, where R and R′ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and a hydrolyzable metal compound having the formula MX′ ｖ wherein M is a metal selected from groups 2 to 16 of the periodic table of the elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof.

[0121] an organic solvent and a solution of the formula RSnO （３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0122] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0123] Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0124] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0125] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0126] The electron beam or EUV irradiation is carried out, for example, through a mask (reticle) for forming a predetermined pattern. The irradiation energy of the electron beam and the exposure dose of the EUV are not particularly limited.

[0127] After irradiation with electron beams or EUV and before development, baking (PEB: Post Exposure Bake) may be performed. The baking temperature is not particularly limited, but is preferably 60° C. to 150° C., more preferably 70° C. to 120° C., and particularly preferably 75° C. to 110° C. The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0128] For example, an alkaline developer or an organic solvent is used for development. The development temperature is, for example, 5°C to 50°C. The development time is, for example, 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, the aqueous solutions of the alkalis may be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like may also be added to these developers. Alternatively, development may be carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the portions of the photoresist where the alkaline dissolution rate is not improved may be developed.

[0129] An organic solvent can be used as a developer for the metal-containing resist, and development is carried out with the developer (solvent) after irradiation with light or electron beams. As a result, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed areas is removed, and a pattern of the metal-containing resist film is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methyl ... -Methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3 -methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate,Examples of the developer include propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can also be added to these developers.

[0130] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. If the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the semiconductor substrate is processed by a known method (e.g., dry etching), thereby manufacturing a semiconductor device.

[0131] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0132] The weight-average molecular weights of the polymers shown in the following Synthesis Examples 1 to 28 and Comparative Synthesis Examples 1 and 2 are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: TSKgel Super-Multipore HZ-N (2 columns) Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0133] Synthesis Example 1 5.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 2.71 g of 5,5-diethylbarbituric acid, 2.02 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.44 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 15.26 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 1. GPC analysis showed that the weight-average molecular weight of the obtained polymer 1 was 3,600 and the dispersity was 2.3, calculated as standard polystyrene. The structure present in polymer 1 is shown in the following formula. The ester bond concentration of polymer 1 was 0.183 g per 1 g of polymer 1.

[0134]

[0135] Synthesis Example 2 5.00 g of o-phthalic acid diglycidyl ester (product name: EX-721, manufactured by Nagase ChemteX Corporation), 2.49 g of 5,5-diethylbarbituric acid, 1.86 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.40 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 14.62 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 2. GPC analysis showed that the weight-average molecular weight of the obtained polymer 2 was 2,500 and the dispersity was 2.5, calculated as standard polystyrene. The structure present in polymer 2 is shown in the following formula. The ester bond concentration of polymer 2 was 0.183 g per 1 g of polymer 2.

[0136]

[0137] Synthesis Example 3 5.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 2.44 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.02 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.44 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 14.86 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 3. GPC analysis showed that the obtained polymer 3 had a weight average molecular weight of 4,200 and a dispersity of 2.7, calculated in terms of standard polystyrene. The structure present in polymer 3 is shown in the following formula. The ester bond concentration of polymer 3 was 0.328 g per 1 g of polymer 3.

[0138]

[0139] Synthesis Example 4 5.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 2.49 g of monoallyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 2.02 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.44 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.04 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 14.99 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 4. GPC analysis revealed that the weight average molecular weight of the obtained polymer 4 was 3,900 and the dispersity was 2.7, calculated as standard polystyrene. The structure present in polymer 4 is shown in the following formula. The ester bond concentration of polymer 4 is 0.188 g per 1 g of polymer 4.

[0140]

[0141] Synthesis Example 5 4.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 2.49 g of 1-allyl-3,5-bis(carboxymethyl)isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.62 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.35 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 0.03 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 6.24 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 5. GPC analysis showed that the resulting polymer 5 had a weight average molecular weight of 3,500 and a polydispersity of 2.2, calculated as standard polystyrene. The structure present in polymer 5 is shown in the following formula. The ester bond concentration of polymer 5 is 0.276 g per 1 g of polymer 5.

[0142]

[0143] Synthesis Example 6 6.00 g of o-phthalic acid diglycidyl ester (trade name: EX-721, manufactured by Nagase ChemteX Corporation), 2.69 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.23 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.49 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 26.61 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 6. GPC analysis showed that the weight average molecular weight of the obtained polymer 6 was 3,100 and the dispersity was 3.2, calculated in terms of standard polystyrene. The structure present in polymer 6 is shown in the following formula. The ester bond concentration of polymer 6 was 0.328 g per 1 g of polymer 6.

[0144]

[0145] Synthesis Example 7 5.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase ChemteX Corporation), 3.45 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.44 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 35.55 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 7. GPC analysis showed that the obtained polymer 7 had a weight average molecular weight of 4,700 and a dispersity of 2.3, calculated in terms of standard polystyrene. The structure present in polymer 7 is shown in the following formula. The ester bond concentration of polymer 7 was 0.405 g per 1 g of polymer 7.

[0146]

[0147] Synthesis Example 8 5.00 g of o-phthalic acid diglycidyl ester (trade name: EX-721, manufactured by Nagase ChemteX Corporation), 3.26 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.42 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 34.72 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 8. GPC analysis showed that the weight average molecular weight of the obtained polymer 8 was 3,600 and the dispersity was 2.5, calculated as standard polystyrene. The structure present in polymer 8 is shown in the following formula. The ester bond concentration of polymer 8 was 0.405 g per 1 g of polymer 8.

[0148]

[0149] Synthesis Example 9 30.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 2.18 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.28 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 4.27 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was purged with nitrogen, and then the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 9. GPC analysis showed that the obtained polymer 9 had a weight average molecular weight of 3,600 and a dispersity of 2.1, calculated as standard polystyrene. The structure present in polymer 9 is shown in the following formula. The ester bond concentration of polymer 9 was 0.224 g per 1 g of polymer 9.

[0150]

[0151] Synthesis Example 10 5.00 g of YX-4000 (product name, manufactured by JER Corporation), 3.14 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.34 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 33.93 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was then purged with nitrogen and reacted at 140°C for 24 hours to obtain a solution containing polymer 10. GPC analysis showed that the obtained polymer 10 had a weight average molecular weight of 4,400 and a dispersity of 1.9, calculated in terms of standard polystyrene. The structure present in polymer 10 is shown in the following formula. The ester bond concentration of polymer 10 was 0.210 g per 1 g of polymer 10.

[0152]

[0153] Synthesis Example 11 4.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 2.68 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.26 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 39.30 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was purged with nitrogen, and the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer 11. GPC analysis showed that the obtained polymer 11 had a weight average molecular weight of 6,000 and a dispersity of 4.3, calculated in terms of standard polystyrene. The structure present in polymer 11 is shown in the following formula. The ester bond concentration of polymer 11 was 0.208 g per 1 g of polymer 11.

[0154]

[0155] Synthesis Example 12 6.06 g of YX-8800 (trade name, manufactured by JER Corporation), 3.40 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.43 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 39.55 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was then purged with nitrogen and reacted at 140°C for 24 hours to obtain a solution containing polymer 12. GPC analysis showed that the obtained polymer 12 had a weight average molecular weight of 4,500 and a dispersity of 2.3, calculated in terms of standard polystyrene. The structure present in polymer 12 is shown in the following formula. The ester bond concentration of polymer 12 was 0.202 g per 1 g of polymer 12.

[0156]

[0157] Synthesis Example 13 30.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.54 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.28 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.28 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 7.91 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 13. GPC analysis showed that the weight-average molecular weight of the obtained polymer 13 was 3,100 and the dispersity was 2.7, calculated as standard polystyrene. The structure present in polymer 13 is shown in the following formula. The ester bond concentration of polymer 13 was 0.166 g per 1 g of polymer 13.

[0158] (* represents a bond.)

[0159] Synthesis Example 14 5.00 g of product name YX-4000 (manufactured by JER Corporation), 1.91 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.58 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.34 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 35.32 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 14. GPC analysis showed that the obtained polymer 14 had a weight average molecular weight of 5,300 and a polydispersity of 3.0, calculated in terms of standard polystyrene. The structure present in polymer 14 is shown in the following formula. The ester bond concentration of polymer 14 was 0.144 g per 1 g of polymer 14.

[0160] (* represents a bond.)

[0161] Synthesis Example 15 3.00 g of EPICLON HP-4770 (manufactured by DIC Corporation), 1.07 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.88 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 46.29 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 15. GPC analysis showed that the obtained polymer 15 had a weight average molecular weight of 7,000 and a polydispersity of 6.1, calculated as standard polystyrene. The structure present in polymer 15 is shown in the following formula. The ester bond concentration of polymer 15 was 0.131 g per 1 g of polymer 15.

[0162] (* represents a bond.)

[0163] Synthesis Example 16 5.00 g of YX-8800 (product name, manufactured by JER Corporation), 1.99 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.65 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 35.96 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 16. GPC analysis showed that the weight average molecular weight of the obtained polymer 16 was 3,300 and the dispersity was 2.9, calculated as standard polystyrene. The structure present in polymer 16 is shown in the following formula. The ester bond concentration of polymer 16 was 0.151 g per 1 g of polymer 16.

[0164] (* represents a bond.)

[0165] Synthesis Example 17 20.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.03 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.36 g of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 2.24 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 17. GPC analysis showed that the obtained polymer 17 had a weight average molecular weight of 4,500 and a dispersity of 2.2, calculated in terms of standard polystyrene. The structure present in polymer 17 is shown in the following formula. The ester bond concentration of polymer 17 was 0.196 g per 1 g of polymer 17.

[0166] (* represents a bond.)

[0167] Synthesis Example 18 20.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.03 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.46 g of 2,3,5-triiodobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 8.48 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 18. GPC analysis showed that the weight-average molecular weight of the obtained polymer 18 was 2,700 and the dispersity was 1.9, calculated as standard polystyrene. The structure present in polymer 18 is shown in the following formula. The ester bond concentration of polymer 18 was 0.156 g per 1 g of polymer 18.

[0168] (* represents a bond.)

[0169] Synthesis Example 19 20.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.03 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.05 g of 2,4,6-tribromobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 6.15 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 19. GPC analysis showed that the obtained polymer 19 had a weight average molecular weight of 4,700 and a polydispersity of 1.9, calculated in terms of standard polystyrene. The structure present in polymer 19 is shown in the following formula. The ester bond concentration of polymer 19 was 0.169 g per 1 g of polymer 19.

[0170] (* represents a bond.)

[0171] Synthesis Example 20 20.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.03 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.53 g of 1-adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 3.20 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 20. GPC analysis showed that the obtained polymer 20 had a weight average molecular weight of 5,500 and a polydispersity of 2.5, calculated as standard polystyrene. The structure present in polymer 20 is shown in the following formula. The ester bond concentration of polymer 20 was 0.188 g per 1 g of polymer 20.

[0172] (* represents a bond.)

[0173] Synthesis Example 21 20.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.03 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.43 g of 4-vinylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 1.49 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 21. GPC analysis showed that the weight average molecular weight of the obtained polymer 21 was 3,800 and the dispersity was 2.0, calculated as standard polystyrene. The structure present in polymer 21 is shown in the following formula. The ester bond concentration of polymer 21 was 0.192 g per 1 g of polymer 21.

[0174] (* represents a bond.)

[0175] Synthesis Example 22 30.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 2.46 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 23.83 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was then purged with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 22. GPC analysis showed that the obtained polymer 22 had a weight average molecular weight of 1,900 and a dispersity of 1.9, calculated in terms of standard polystyrene. The structure present in polymer 22 is shown in the following formula. The ester bond concentration of polymer 22 was 0.231 g per 1 g of polymer 22.

[0176]

[0177] Synthesis Example 23 15.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 0.81 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.28 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 20.04 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 23. GPC analysis showed that the weight-average molecular weight of the obtained polymer 23 was 1,500 and the dispersity was 1.7, calculated as standard polystyrene. The structure present in polymer 23 is shown in the following formula. The ester bond concentration of polymer 23 was 0.155 g per 1 g of polymer 23.

[0178] (* represents a bond.)

[0179] Synthesis Example 24 15.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 0.81 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.64 g of 2,3,5-triiodobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 23.28 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 24. GPC analysis showed that the weight-average molecular weight of the obtained polymer 24 was 1,600 and the dispersity was 1.5, calculated as standard polystyrene. The structure present in polymer 24 is shown in the following formula. The ester bond concentration of polymer 24 was 0.146 g per 1 g of polymer 24.

[0180] (* represents a bond.)

[0181] Synthesis Example 25 25.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.29 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.62 g of 5-nitroisophthalic acid monomethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.23 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 3.76 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 25. GPC analysis showed that the weight average molecular weight of the obtained polymer 25 was 4,200 and the dispersity was 2.2, calculated as standard polystyrene. The structure present in polymer 25 is shown in the following formula. The ester bond concentration of polymer 25 was 0.210 g per 1 g of polymer 25.

[0182] (* represents a bond.)

[0183] Synthesis Example 26 25.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 1.29 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of 3-nitrobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.23 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 2.86 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 26. GPC analysis showed that the obtained polymer 26 had a weight average molecular weight of 4,200 and a polydispersity of 2.1, calculated as standard polystyrene. The structure present in polymer 26 is shown in the following formula. The ester bond concentration of polymer 26 was 0.190 g per 1 g of polymer 26.

[0184] (* represents a bond.)

[0185] Synthesis Example 27 19.00 g of EPICLON WR-400 (trade name, manufactured by DIC Corporation, 10 wt % propylene glycol monomethyl ether solution), 0.98 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.37 g of 4-tert-butylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.18 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 2.31 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 27. GPC analysis showed that the weight average molecular weight of the obtained polymer 27 was 5,300 in terms of standard polystyrene, and the dispersity was 2.5. The structure present in polymer 27 is shown in the following formula. The ester bond concentration of polymer 27 was 0.188 g per 1 g of polymer 27.

[0186] (* represents a bond.)

[0187] Synthesis Example 28 4.00 g of EPICLON HP-4032D (manufactured by DIC Corporation), 2.04 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.08 g of 3,5-di-tert-butyl-4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.37 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 11.24 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 140°C for 24 hours to obtain a solution containing polymer 28. GPC analysis showed that the weight average molecular weight of the obtained polymer 28 was 3,700 and the dispersity was 3.3, calculated as standard polystyrene. The structure present in polymer 28 is shown in the following formula. The ester bond concentration of polymer 28 was 0.180 g per 1 g of polymer 28.

[0188] (* represents a bond.)

[0189] Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved therein. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 130°C for 24 hours to obtain a solution containing Comparative Polymer 1. GPC analysis showed that the obtained Comparative Polymer 1 had a weight average molecular weight of 6,800 and a dispersity of 4.8, calculated in terms of standard polystyrene. The structure present in Comparative Polymer 1 is shown in the following formula. The ester bond concentration of Comparative Polymer 1 was 0 g per 1 g of Comparative Polymer 1.

[0190]

[0191] Comparative Synthesis Example 2 6.00 g of resorcinol diglycidyl ether (product name: EX-201-IM, manufactured by Nagase ChemteX Corporation), 3.97 g of 5,5-diethylbarbituric acid, 2.97 g of 3,5-diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.64 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 31.63 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The reaction vessel was then purged with nitrogen and reacted at 140°C for 24 hours to obtain a solution containing Comparative Polymer 2. GPC analysis showed that the obtained Comparative Polymer 2 had a weight average molecular weight of 2,900 and a polydispersity of 2.9, calculated as standard polystyrene. The structure present in Comparative Polymer 2 is shown in the following formula. The ester bond concentration of Comparative Polymer 2 was 0.027 g per 1 g of Comparative Polymer 2.

[0192]

[0193] (Preparation of Resist Underlayer) (Examples, Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 28 and Comparative Synthesis Examples 1 and 2 were mixed in the proportions shown in Tables 1-1, 1-2, and 2, and filtered through a 0.1 μm fluororesin filter to prepare compositions for forming resist underlayer films. The amounts of each additive are shown in parts by mass, and the amount of the solvent is shown in composition ratio.

[0194] The abbreviations in Tables 1-1, 1-2, and 2 are as follows: PL-LI: tetramethoxymethylglycoluril PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- (structural formula below)

[0195] PyPSA: Pyridinium-p-hydroxybenzenesulfonic acid PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0196]

[0197]

[0198]

[0199] (Elution test into photoresist solvent) Each of the resist underlayer film-forming compositions of Examples 1 to 28 and Comparative Examples 1 and 2 was applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30 (volume ratio), which is a solvent used in photoresists. A change in film thickness of less than 5 Å was rated as "good", and a change in film thickness of 5 Å or more was rated as "poor". The results are shown in Table 3.

[0200]

[0201] (Resist Patterning Evaluation) [Resist Pattern Formation Test Using EUV Exposure Apparatus] The resist underlayer film-forming compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a thickness of 5 nm. An EUV positive resist solution was spin-coated onto the resist underlayer film and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an EUV exposure apparatus (NXE3400B). After exposure, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer. Resist patterns with line sizes of 10 nm to 21 nm were formed. A scanning electron microscope (CG6300, manufactured by Hitachi High-Technologies Corporation) was used to measure the length of the resist pattern. The photoresist patterns thus obtained were evaluated for the possibility of forming 18 nm lines and spaces (L / S). Formation of 18 nm L / S patterns was confirmed in all cases of Examples 1 to 6 and Comparative Examples 1 and 2. The EUV irradiation dose that formed the 18 nm L / S pattern was defined as the optimal irradiation energy, and the irradiation energy (mJ / cm) at that time was ２ ), and LWR (line width roughness) are shown in Table 4. In Examples 1 to 6, an improvement in LWR was confirmed compared with Comparative Examples 1 and 2.

[0202]

[0203] (Resist Patterning Evaluation) [Resist Pattern Formation Test Using Electron Beam Lithography Apparatus] The resist underlayer film-forming compositions of Examples 7 to 28 and Comparative Example 1 were each applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a 5 nm-thick resist underlayer film. An EUV positive resist solution was spin-coated onto the resist underlayer film and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was irradiated with EB under specified conditions using an electron beam lithography apparatus (ELS-G130). After irradiation, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer. Resist patterns with line sizes of 16 nm to 28 nm were formed. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the length of the resist pattern. The photoresist patterns thus obtained were evaluated for the possibility of forming a line and space (L / S) pattern (L / S = 1 / 1.3) with 24 nm lines and 56 nm pitch. Formation of an L / S pattern with 24 nm lines and 56 nm pitch was confirmed in Examples 7 to 28. The charge amount at which an L / S pattern with 24 nm lines and 56 nm pitch was formed was defined as the optimal irradiation energy, and the irradiation energy (μC / cm ２ ), and LWR are shown in Table 5. Improvements in LWR and minimum CD size were confirmed in Examples 7 to 28 compared to Comparative Example 1. The minimum CD size indicates the limit CD size at which no pattern collapse occurs, and the LWR indicates the value at 24 nm line / 56 nm pitch.

[0204]

[0205] The resist underlayer film-forming composition according to the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, as well as a method for producing a substrate having a resist pattern and a method for producing a semiconductor device using the resist underlayer film-forming composition.

Claims

1. A composition for forming a resist underlayer film used in electron beam lithography or EUV lithography, comprising a polymer having a structural unit represented by the following formula (1), and a solvent: (In formula (1), each A independently represents a hydrogen atom, a methyl group, or an ethyl group. Q represents a divalent group. X represents a hydrogen atom or a nitro group.) 2. The composition for forming a resist underlayer film according to claim 1, wherein Q in the formula (1) is represented by the following formula (1-1) or formula (1-2): (In formula (1-1), Q １ represents a divalent organic group having 1 to 30 carbon atoms. n1 and n2 each independently represent 0 or 1. In formula (1-2), X １ represents a group represented by any one of the following formulas (1-2-1) to (1-2-3). １ and Z ２ each independently represents a single bond or a group represented by the following formula (1-2-4). * represents a bond. (In formulas (1-2-1) to (1-2-3), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy 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 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each independently be substituted with a group or atom 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, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond bonding to a carbon atom in formula (1-2). *2 represents a bond bonding to a nitrogen atom in formula (1-2). (In formula (1-2-4), m represents an integer of 1 to 4. n represents an integer of 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond bonding to the nitrogen atom in formula (1-2). *4 represents a bond.) 3. The composition for forming a resist underlayer film according to claim 1, wherein the polymer has a structure represented by the following formula (E) at its terminal. (In formula (E), E represents a group having 1 to 20 carbon atoms, n represents 0 or 1, and * represents a bond.) 4. The composition for forming a resist underlayer film according to claim 3, wherein E in formula (E) represents a monovalent group having a ring structure.

5. The composition for forming a resist underlayer film according to claim 1, wherein the concentration of ester bonds in the polymer is 0.030 g to 0.340 g per 1 g of the polymer.

6. The composition for forming a resist underlayer film according to claim 1, wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

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 7, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

9. The composition for forming a resist underlayer film according to claim 1, further comprising a curing catalyst.

10. A resist underlayer film, which is a cured product of the composition for forming a resist underlayer film according to any one of claims 1 to 9.

11. A laminate comprising: a semiconductor substrate; and the resist underlayer film according to claim 10.

12. A method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 9; and a step of forming a resist film on the resist underlayer film.

13. A pattern formation method comprising: a step of forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 9; a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with an electron beam or EUV and then developing the resist film to obtain a resist pattern; and a step of etching the resist underlayer film using the resist pattern as a mask.

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