Composition for forming EUV resist underlayer film

Abstract

The present invention provides a composition for forming an underlayer film of a resist capable of forming a desired resist pattern, a method for manufacturing a resist pattern using the composition for forming an underlayer film of a resist, and a method for manufacturing a semiconductor device. An EUV resist underlayer film forming composition comprising: the following formula (1): (In formula (1), Y 1 represents an alkylene group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, T 1 and T 2 each independently represents a hydroxyl group or a carboxyl group, R 1 and R 2 each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and n1 and n2 each independently represent an integer of 0 to 4) a reaction product of the compound shown and a diepoxide compound; and an organic solvent.

Description

Technical Field

[0001] The present invention relates to a composition used in a lithography process in semiconductor manufacturing, particularly in the lithography processes at the forefront (such as ArF, EUV, EB, etc.). Furthermore, it relates to a method for manufacturing a substrate with a resist pattern to which the above-mentioned underlayer resist film is applied, and a method for manufacturing a semiconductor device. Background Art

[0002] Hitherto, in the manufacture of semiconductor devices, fine processing has been carried out by lithography using a resist composition. The above-mentioned fine processing is a method of forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating active light such as ultraviolet light through a mask pattern depicting a device pattern thereon, developing, and using the resulting photoresist pattern as a protective film to etch the substrate, thereby forming fine irregularities corresponding to the above pattern on the substrate surface. In recent years, with the progress of high integration of semiconductor devices, in addition to the conventionally used i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) has been studied in the forefront fine processing. In order to control the shape of the resist pattern, a method of forming an underlayer resist film layer between the resist and the semiconductor substrate has been widely used.

[0003] Patent Document 1 discloses an additive for a composition for forming an underlayer resist film containing a copolymer containing fluorine atoms. Patent Document 2 discloses a polymer used in a composition for forming an underlayer resist film containing a structural unit containing fluorine atoms.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2010 / 074075

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2015-143360 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] As characteristics required for an underlayer resist film, for example, non-mixing with the resist film formed on the upper layer (insoluble in the resist solvent) and a faster dry etching rate compared to the resist film can be cited.

[0010] In the case of lithography accompanied by EUV exposure, the line width of the formed resist pattern becomes 32 nm or less, and the underlayer film for EUV exposure is formed with a thinner film thickness than in the past. When forming such a thin film, due to the influence of the substrate surface, the polymers used, etc., pinholes, aggregation, etc. are likely to occur, and it is difficult to form a uniform film without defects.

[0011] On the other hand, when forming a resist pattern, in the development process, a method is sometimes adopted in which the unexposed portion of the resist film is removed using a solvent capable of dissolving the resist film, usually an organic solvent, and the exposed portion of the resist film is left as a resist pattern. In such a negative development process, improving the adhesion of the resist pattern becomes a major issue.

[0012] In addition, it is required to suppress the deterioration of LWR (Line Width Roughness, line width roughness, fluctuation of line width (roughness)) during the formation of the resist pattern, to form a resist pattern with a good rectangular shape, and to improve the resist sensitivity.

[0013] An object of the present invention is to provide a composition for forming an underlayer film of a resist that solves the above problems and can form a desired resist pattern, and a method for forming a resist pattern using the composition for forming the underlayer film of the resist.

[0014] Means for solving the problems

[0015] The present invention includes the following aspects.

[0016] [1] A composition for forming an EUV resist underlayer film, comprising:

[0017] A reaction product of a compound represented by the following formula (1) and a diepoxide; and

[0018] An organic solvent.

[0019]

[0020] (In formula (1),

[0021] Y 1 represents an alkylene group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom,

[0022] T 1 and T 2 each independently represent a hydroxyl group or a carboxyl group,

[0023] R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, and n1 and n2 each independently represent an integer of 0 to 4)

[0024] [2] In the composition for forming an EUV resist underlayer film according to [1], the above Y 1 is an alkylene group having 1 to 10 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms.

[0025] [3] In the composition for forming an EUV resist underlayer film according to [1] or [2], the above reaction product contains structural units derived from the compound represented by formula (1) at a molar ratio of 50 mol% or more.

[0026] [4] The composition for forming an EUV resist underlayer film according to any one of [1] to [3] further contains a crosslinking agent.

[0027] [5] The composition for forming an EUV resist underlayer film according to any one of [1] to [4] further contains a crosslinking catalyst.

[0028] [6] In the composition for forming an EUV resist underlayer film according to any one of [1] to [5], the above diepoxide is a compound containing a heterocycle.

[0029] [7] An EUV resist underlayer film, characterized in that it is a fired product of a coating film formed from the composition for forming an EUV resist underlayer film according to any one of [1] to [6].

[0030] [8] A method for manufacturing a patterned substrate, comprising the following steps: a step of coating the composition for forming an EUV resist underlayer film according to any one of [1] to [6] on a semiconductor substrate and baking to form an EUV resist underlayer film; a step of coating an EUV resist on the above EUV resist underlayer film and baking to form an EUV resist film; a step of exposing the semiconductor substrate covered with the above EUV resist underlayer film and the above EUV resist; and a step of developing the exposed EUV resist film to form a pattern.

[0031] [9] A method for manufacturing a semiconductor device, characterized in that it comprises the following steps:

[0032] A step of forming an EUV resist underlayer film formed from the composition for forming an EUV resist underlayer film according to any one of [1] to [6] on a semiconductor substrate;

[0033] A step of forming an EUV resist film on the above EUV resist underlayer film;

[0034] A step of forming an EUV resist pattern by irradiation of light or electron rays on the EUV resist film and subsequent development;

[0035] A step of forming a patterned EUV resist underlayer film by etching the above EUV resist underlayer film through the above-formed EUV resist pattern; and

[0036] A step of processing a semiconductor substrate using the patterned EUV resist underlayer film.

[0037] Effects of the Invention

[0038] The EUV resist underlayer film-forming composition of the present application can particularly achieve suppression of deterioration of LWR during resist pattern formation and improvement of sensitivity by having such a configuration. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 1H-NMR spectrum of the polymer obtained in Synthesis Example 1 1 1H-NMR spectrum. DETAILED DESCRIPTION OF THE INVENTION

[0040] <EUV Resist Underlayer Film-Forming Composition>

[0041] The EUV resist underlayer film-forming composition of the present invention contains a reaction product of a compound represented by the following formula (1) and a diepoxide, and an organic solvent.

[0042]

[0043] (In formula (1), Y 1 represents an alkylene group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, T 1 and T 2 each independently represent a hydroxyl group or a carboxyl group, R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and n1 and n2 each independently represent an integer of 0 to 4)

[0044] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylidene, cyclopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl-cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4-dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene or n-decylene.

[0045] Examples of the alkyl group having 1 to 10 carbon atoms described above include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, sropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl.

[0046] Preferably, the above Y 1 is an alkylene group having 1 to 10 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms. Preferably, the above Y 1 is a group represented by the following formula.

[0047] -C(CF3)2-

[0048] Preferably, both n1 and n2 are 0 (zero).

[0049] Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas, but are not limited to them.

[0050]

[0051] <Diepoxide>

[0052] The composition for forming an underlayer film for EUV resist of the present application contains a reaction product (copolymer) obtained by reacting the compound represented by the above formula (1) with a diepoxide by a known method.

[0053] As the above diepoxide, as long as it is a compound having two epoxy groups in the molecule, there is no particular limitation, but a compound containing a heterocycle is preferably included.

[0054] The molar ratio of the compound represented by the above formula (1) to the diepoxide during the reaction is, for example, 50:50 to 30:70.

[0055] Preferably, the molar ratio of the compound represented by the formula (1) in the above reaction product is 50 mol% or more, 60 mol% or more, 70 mol% or more. The sensitivity during EUV resist exposure brought about by the fluorine atoms contained in the compound represented by the formula (1) can be increased.

[0056] The fluorine content (wt%) relative to the whole of the above reaction product is preferably 10 wt% or more, more preferably 15 wt% or more. The upper limit is, for example, 50 wt%.

[0057] The weight average molecular weight of the reaction product (polymer) is, for example, 2,000 to 50,000. The above weight average molecular weight can be measured, for example, by gel permeation chromatography described in the examples.

[0058] The proportion of the above reaction product contained relative to the whole composition for forming an underlayer film for EUV resist of the present application is preferably 0.1 wt% to 1.0 wt%.

[0059] As specific examples of the compound used for manufacturing the reaction product of the present application, compounds represented by the following formulae can be cited, but are not limited to them.

[0060]

[0061] <Organic solvent>

[0062] Examples of the organic solvent contained in the composition for forming an EUV resist underlayer film of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 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. These solvents can be used alone or in combination of two or more kinds.

[0063] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0064] <Crosslinking agent>

[0065] Examples of the crosslinking agent contained as an optional component in the composition for forming an EUV resist underlayer film of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetra(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetra(butoxymethyl)glycoluril, 1,3,4,6-tetra(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl)urea, and 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine ((trade name) Cymel [registered trademark]-303, Nikalac [registered trademark] MW-390).

[0066] In addition, the crosslinking agent of the present application may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1X) bonded to a nitrogen atom as described in WO2017 / 187969.

[0067]

[0068] (In formula (1X), R1 represents a methyl group or an ethyl group.)

[0069] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1X) in the molecule may be a glycoluril derivative represented by the following formula (1A).

[0070]

[0071] (In formula (1A), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0072] As the glycoluril derivative represented by the above formula (1A), for example, compounds represented by the following formulas (1A-1) to (1A-6) can be cited.

[0073]

[0074] The compound represented by the above formula (1A) can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2) bonded to a nitrogen atom with at least one compound represented by the following formula (3) to produce a nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1X) in the molecule.

[0075]

[0076] (In formulas (2) and (3), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.)

[0077] The glycoluril derivative represented by the above formula (1A) can be obtained by reacting a glycoluril derivative represented by the following formula (2A) with at least one compound represented by the above formula (3).

[0078] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2) in the molecule is, for example, a glycoluril derivative represented by the following formula (2A).

[0079]

[0080] (In formula (2A), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4s each independently represent an alkyl group having 1 to 4 carbon atoms.)

[0081] As the glycoluril derivative represented by the above formula (2A), for example, compounds represented by the following formulas (2A-1) to (2A-4) can be cited. Further, as the compound represented by the above formula (3), for example, compounds represented by the following formulas (3-1) and (3-2) can be cited.

[0082]

[0083] Regarding the nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1X) bonded to a nitrogen atom in the above-mentioned 1 molecule, it is based on the content described in WO2017 / 187969.

[0084] When using the above crosslinking agent, the content ratio of the crosslinking agent relative to the above polymer is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass.

[0085] <Crosslinking catalyst (curing catalyst)>

[0086] As the crosslinking catalyst (curing catalyst) optionally contained in the composition for forming an EUV resist underlayer film of the present invention, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine -p-toluenesulfonate (pyridine -p-toluenesulfonic acid), pyridine -p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridine -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 and other sulfonic acid compounds and carboxylic acid compounds can be mentioned. When using the above crosslinking catalyst, the content ratio of the crosslinking catalyst relative to the above crosslinking agent is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass.

[0087] <Other components>

[0088] In the composition for forming an underlayer film of a resist of the present invention, in order to prevent the generation of pinholes, streaks, etc. and further improve the coatability on an uneven surface, a surfactant may be further added. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and other nonionic surfactants; fluorine-based surfactants such as EFtop EF301, EF303, EF352 (manufactured by Tocem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals, Inc., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited, trade name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name); and silicone oxide polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on all the solid components of the composition for forming an underlayer film of a resist of the present invention. These surfactants may be added alone, or may be added in combination of two or more kinds.

[0089] <EUV Resist Underlayer Film>

[0090] The EUV resist underlayer film of the present invention can be manufactured by coating the above composition for forming an underlayer film of an EUV resist on a semiconductor substrate and then baking it.

[0091] Examples of the semiconductor substrate for coating the composition for forming an underlayer film of a resist of the present invention include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0092] In the case of a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed, for example, by an ALD (Atomic Layer Deposition) method, a CVD (Chemical Vapor Deposition) method, a reactive sputtering method, an ion plating method, a vacuum evaporation method, or a spin coating method (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 oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0093] On such a semiconductor substrate, the composition for forming an underlayer film of a resist of the present invention is coated by an appropriate coating method such as a spinner or a coater. Then, baking is performed using a heating means such as a hot plate to form an underlayer film of a resist. As the baking conditions, appropriate selection is made from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0094] The film thickness of the formed EUV resist underlayer film is, 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 (1 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm). When the temperature during baking is lower than the above range, crosslinking becomes insufficient. On the other hand, when the temperature during baking is higher than the above range, the underlayer film of the resist may be decomposed by heat.

[0095] <Method for manufacturing a substrate having a pattern formed thereon, method for manufacturing a semiconductor device>

[0096] The manufacturing method of a substrate on which a pattern is formed goes through the following processes. Generally, it is manufactured by forming a photoresist layer on an EUV resist underlayer film. As the photoresist formed by coating and baking on the EUV resist underlayer film by a method known per se, there is no particular limitation as long as it is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used. There are positive photoresists composed of novolak resin and 1,2-naphthoquinone diazide sulfonate, chemically amplified photoresists composed of a binder having a group that increases the alkali dissolution rate by decomposition with acid and a photoacid generator, chemically amplified photoresists composed of a low molecular compound that increases the alkali dissolution rate of the photoresist by decomposition with acid, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists composed of a binder having a group that increases the alkali dissolution rate by decomposition with acid, a low molecular compound that increases the alkali dissolution rate of the photoresist by decomposition with acid, and a photoacid generator, resists containing a metal element, etc. For example, products with trade names V146G manufactured by JSR Corporation, APEX-E manufactured by Shipley Company, PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. can be cited. In addition, for example, fluorine atom-containing polymer-based photoresists as described in Proc. SPIE, Vol. 3999, 330 - 334 (2000), Proc. SPIE, Vol. 3999, 357 - 364 (2000), Proc. SPIE, Vol. 3999, 365 - 374 (2000) can be cited.

[0097] In addition, so-called resist compositions such as resist compositions, radiation-sensitive resin compositions, compositions for forming high-resolution patterns based on organometallic solutions, and metal-containing resist compositions described in WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP-A-2018-180525, WO2018 / 190088, JP-A-2018-070596, JP-A-2018-028090, JP-A-2016-153409, JP-A-2016-130240, JP-A-2016-108325, JP-A-2016-047920, JP-A-2016-035570, JP-A-2016-035567, JP-A-2016-035565, JP-A-2019-101417, JP-A-2019-117373, JP-A-2019-052294, JP-A-2019-008280, JP-A-2019-008279, JP-A-2019-003176, JP-A-2019-003175, JP-A-2018-197853, JP-A-2019-191298, JP-A-2019-061217, JP-A-2018-045152, JP-A-2018-022039, JP-A-2016-090441, JP-A-2015-10878, JP-A-2012-168279, JP-A-2012-022261, JP-A-2012-022258, JP-A-2011-043749, JP-A-2010-181857, JP-A-2010-128369, WO2018 / 031896, JP-A-2019-113855, WO2017 / 156388, WO2017 / 066319, JP-A-2018-41099, WO2016 / 065120, WO2015 / 026482, JP-A-2016-29498, JP-A-2011-253185, etc. are used, but not limited to them.

[0098] Examples of the resist composition include, for example, the following resist compositions.

[0099] (i) A chemically amplified resist composition containing a resin A and a compound represented by the general formula (11), wherein the resin A has a repeating unit having an acid-decomposable group in which a polar group is protected by a protecting group that is cleaved by the action of an acid.

[0100]

[0101] In the general formula (11), m represents an integer of 1 to 6.

[0102] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0103] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0104] L2 represents an alkylene group which may have a substituent or a single bond.

[0105] W1 represents a cyclic organic group which may have a substituent.

[0106] M + represents a cation.

[0107] (ii) A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, which contains a compound having a metal-oxygen covalent bond and a solvent, and the metal element constituting the compound belongs to the 3rd to 15th groups and the 3rd to 7th periods of the periodic table.

[0108] (iii) A radiation-sensitive resin composition containing a polymer and an acid generator, wherein the polymer has a first structural unit represented by the following formula (21) and a second structural unit represented by the following formula (22) and containing an acid-dissociable group.

[0109]

[0110] (In the formula (21), Ar is a group obtained by removing (n + 1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. R 1 is a hydroxyl 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, a plurality of R 1 are the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0111] In the formula (22), R 3is 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 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. )

[0112] (iv) A resist composition containing a resin (A1) and an acid generator, wherein the resin (A1) contains a structural unit having a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit having an acid labile group.

[0113]

[0114] [In formula (II),

[0115] 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 -*, where * represents a bonding bond with -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 a hydroxyl group and a carboxyl group. ]

[0116] (v) A resist composition characterized in that it generates an acid upon exposure and changes its solubility in a developer by the action of the acid,

[0117] which contains a substrate component (A) whose solubility in a developer changes by the action of an acid and a fluorine additive component (F) that is decomposable in an alkaline developer.

[0118] The fluorine additive component (F) contains a fluororesin component (F1), and the fluororesin component (F1) has a structural unit (f1) containing an alkali dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0119]

[0120] [In formula (f2-r-1), Rf 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n” is an integer from 0 to 2. * is a bonding bond. ]

[0121] (vi) The resist composition according to the above (v), wherein the structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0122]

[0123] [In formula (f1-1) and formula (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable moiety. A aryl is a divalent aromatic cyclic group which may have a substituent. X 01 is a single bond or a divalent linking group. R 2 are each independently an organic group having a fluorine atom.]

[0124] As a metal-containing resist composition, for example, a coating material containing a metal oxy-hydroxy network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond can be cited.

[0125] (vii) An inorganic oxygen / hydroxy-based composition.

[0126] As a resist film, for example, the following resist films can be cited.

[0127] (i) A resist film containing a base resin, the base resin containing a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.

[0128]

[0129] (In formula (a1) and formula (a2), R A are each independently a hydrogen atom or a methyl group. R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms. R 3 are each independently a fluorine atom or a methyl group. m is an integer of 0 to 4. X 1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. X 2 is a single bond, an ester bond, or an amide bond.)

[0130] As a resist material, for example, the following resist materials can be cited.

[0131] (i) A resist material containing a polymer having a repeating unit represented by the following formula (a1) or (a2).

[0132]

[0133] (In formula (a1) and formula (a2), R A is a hydrogen atom or a methyl group. X 1 is a single bond or an ester group. X 2is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms. A part of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring. Further, X 2 at least one hydrogen atom contained therein is substituted with a bromine atom. X 3 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms. A part of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, provided that at least one of them is a fluorine atom or a trifluoromethyl group. Further, Rf 1 and Rf 2 may combine to form a carbonyl group. R 1 to 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. A part or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfo group or a group containing a sulfonium salt. A part 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 group. Further, R 1 and R 2 may combine to form a ring together with the sulfur atom to which they are attached.)

[0134] (ii) A resist material comprising a base resin, wherein the base resin comprises: a polymer containing a repeating unit represented by the following formula (a).

[0135]

[0136] (In formula (a), R A is a hydrogen atom or a methyl group. R 1 is a hydrogen atom or an acid-labile group. R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a halogen atom other than bromine. X 1 is a single bond or 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. X 2 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. n is an integer of 0 to 3.)

[0137] Examples of the coating solution include, for example, the following coating solutions. Examples include:

[0138] (i) A coating solution comprising: an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; and a hydrolyzable metal compound represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0139] (ii) A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), containing from about 0.0025 M to about 1.5 M of tin in the above solution, R being an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the above alkyl or cycloalkyl group being bonded to tin at a secondary or tertiary carbon atom).

[0140] (iii) An aqueous solution of an inorganic pattern-forming precursor comprising water, a metal lower oxide cation, a polyatomic inorganic anion, and a mixture with a radiation-sensitive ligand, the above radiation-sensitive ligand containing a peroxide group. And so on.

[0141] Exposure is performed through a mask (reticle) for forming a prescribed pattern, using, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam). However, the composition for forming an underlayer film of a resist of the present application is preferably applied to EUV (extreme ultraviolet) exposure. Development is performed using an alkaline developer, appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As the alkaline developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used. Further, alcohols such as isopropanol and surfactants such as nonionic surfactants can be appropriately added to the aqueous solution of the above-mentioned bases and used. Among them, a preferred developer is a quaternary ammonium salt, and more preferably tetramethylammonium hydroxide and choline. Further, a surfactant or the like can be added to these developers. Instead of using an alkaline developer, development can also be performed using an organic solvent such as butyl acetate to develop the portion where the base dissolution rate of the photoresist is not increased. Through the above steps, a substrate with the resist patterned can be manufactured.

[0142] Next, using the formed resist pattern as a mask, dry etching is performed on the above-mentioned underlayer film of the resist. At this time, when the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. When the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, through the step of processing the substrate by a method known per se (dry etching method, etc.), a semiconductor device can be manufactured.

[0143] Examples

[0144] Next, examples are given to specifically illustrate the content of the present invention, but the present invention is not limited thereto.

[0145] The weight average molecular weight of the polymers shown in the following synthesis examples and comparative synthesis examples in this specification is the measurement result obtained by gel permeation chromatography (hereinafter, simply referred to as GPC). The measurement is performed using a GPC device manufactured by Tosoh Corporation, and the measurement conditions are as described below.

[0146] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.)

[0147] Column temperature: 40°C

[0148] Solvent: Tetrahydrofuran (THF)

[0149] Flow rate: 1.0 ml / min

[0150] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0151] <Synthesis Example 1>

[0152] 7.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 10.76 g of 2,2,2-bis(4-carboxyphenyl)hexafluoropropane (molar ratio added is 46:54), and 0.30 g of tetrabutylammonium bromide (manufactured by ACROS) (manufactured by ACROS) were added to 27.09 g of propylene glycol monomethyl ether and dissolved. After replacing the reaction vessel with nitrogen, the mixture was reacted at 90 °C for 24 hours to obtain a polymer solution. This polymer solution did not become cloudy even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and as a result, the polymer in the obtained solution had a weight-average molecular weight of 5000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (2a).

[0153]

[0154] By 1 1H-NMR measurement (JEOL, 500 MHz) of the polymer obtained in Synthesis Example 1 above, the ratio of (1a) and (2a) was calculated. Regarding the measurement sample, 1.00 g of deuterated chloroform (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 0.5 g of the polymer solution containing 0.07 g of the polymer obtained in Synthesis Example 1 above, and sample preparation was carried out. The measurement was performed with a sample tube: 5 mm, solvent: deuterated chloroform, measurement temperature: room temperature, pulse interval: 5 seconds, number of accumulations: 256 times, and reference sample: tetramethylsilane (TMS). This 1 1H-NMR spectrum is shown in Figure 1 .

[0155] 1 1H-NMR (500 MHz): 4.82 (d, 1H), 4.94 (d, 1H), 5.88 ppm (s, 1H), 7.09 ppm (d, 4H), 7.75 ppm (d, 4H)

[0156] The molar ratio of (1a) and (2a) is 50:50.

[0157] <Synthesis Example 2>

[0158] 7.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 8.80 g of 2,2,2-bis(4-hydroxyphenyl)hexafluoropropane (added molar ratio of 46:54), and 0.30 g of tetrabutylammonium bromide (manufactured by ACROSS Co., Ltd.) were added to 27.09 g of propylene glycol monomethyl ether and dissolved. After replacing the reaction vessel with nitrogen, the mixture was reacted at 105 °C for 24 hours to obtain a polymer solution. This polymer solution did not become cloudy even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and as a result, the polymer in the obtained solution had a weight-average molecular weight of 14,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (3a).

[0159]

[0160] <Comparative Synthesis Example 1>

[0161] 8.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5.45 g of barbital (manufactured by Yashiro Pharmaceutical Co., Ltd.), and 0.48 g of tetrabutylammonium bromide (added molar ratio of 46:54) were added to 56.00 g of propylene glycol monomethyl ether and dissolved. After replacing the reaction vessel with nitrogen, the mixture was reacted under reflux for 10 hours to obtain a polymer solution. This polymer solution did not become cloudy even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and as a result, the polymer in the obtained solution had a weight-average molecular weight of 1,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0162]

[0163] <Example 1>

[0164] To 3.12 g of the polymer solution containing 0.47 g of the polymer obtained in the above Synthesis Example 1, 0.11 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.012 g of pyridinium p-phenolsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 263.41 g of propylene glycol monomethyl ether and 29.89 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, filtration was performed using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an underlayer film of a photoresist.

[0165] <Example 2>

[0166] In 3.12 g of the polymer solution containing 0.47 g of the polymer obtained in Synthesis Example 2 above, 0.11 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.012 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 263.41 g of propylene glycol monomethyl ether and 29.89 g of propylene glycol monomethyl ether acetate were added thereto to dissolve them. Then, filtration was performed using a polyethylene microfilter having a pore size of 0.05 μm to prepare a composition for forming an underlayer film of a photoresist.

[0167] <Comparative Example 1>

[0168] In 3.12 g of the polymer solution containing 0.047 g of the polymer obtained in Comparative Synthesis Example 1 above, 0.11 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.012 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 263.41 g of propylene glycol monomethyl ether and 29.89 g of propylene glycol monomethyl ether acetate were added thereto to dissolve them. Then, filtration was performed using a polyethylene microfilter having a pore size of 0.05 μm to prepare a composition for forming an underlayer film of a photoresist.

[0169] [Dissolution test in a photoresist solvent]

[0170] The compositions for forming an underlayer film of a photoresist of Examples 1 and 2 and Comparative Example 1 were respectively coated on a silicon wafer as a semiconductor substrate by a spinner. The silicon wafer was placed on a hot plate and baked at 215°C for 1 minute to form an underlayer film of a photoresist (film thickness: 5 nm). These underlayer films of a photoresist were immersed in ethyl lactate and propylene glycol monomethyl ether, which are solvents used as a photoresist, and it was confirmed that they were insoluble in these solvents.

[0171] [Formation of a resist pattern using an electron beam lithography apparatus]

[0172] The resist underlayer film-forming compositions of Example 1, Example 2, and Comparative Example 1 were respectively coated on silicon wafers using a spin coater. The silicon wafers were baked on a hot plate at 205 °C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. On this resist underlayer film, a positive resist solution for EUV (containing a methacrylic acid-based polymer) was spin-coated and heated at 130 °C for 60 seconds to form an EUV resist film. For this resist film, an electron beam lithography apparatus (ELS-G130) was used to expose it under specified conditions. After exposure, baking (PEB) was performed at 100 °C for 60 seconds, cooled on a cooling plate until room temperature, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with a 25 nm line / 50 nm pitch. The line length measurement of the resist pattern was performed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100). In the formation of the above resist pattern, the exposure amount for forming a 25 nm line / 50 nm pitch (line and space (L / S = 1 / 1)) was set as the optimum exposure amount.

[0173] Regarding the photoresist pattern obtained by such operations, observation from the upper part of the pattern was performed for evaluation. The exposure amounts required to form a 25 nm line of the resist pattern are shown in Table 1.

[0174] [Table 1]

[0175] Table 1

[0176] Exposure dose of 25nm pattern Standard value of exposure dose Fluorine content (mass %) (calculated value) Example 1 570 μC 0.94 19.3 Example 2 562 μC 0.93 17.6 Comparative Example 1 606 μC 1.00 0

[0177] Industrial Applicability

[0178] 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, a method for manufacturing a substrate with a resist pattern using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device.

Claims

1. A composition for forming an EUV resist underlayer film, comprising: A reaction product of a compound represented by the following formula (1) and a diepoxide; and An organic solvent, In formula (1), Y 1 an alkylene group having 1 to 10 carbon atoms in which at least 1 hydrogen atom is replaced by a fluorine atom T 1 and T 2 each independently represents a hydroxyl group or a carboxyl group, R 1 and R 2 each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, n1 and n2 each independently represent an integer of 0 to 4.

2. The composition for forming an EUV resist underlayer film according to claim 1, wherein the Y 1 is an alkylene group having 1 to 10 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms.

3. The composition for forming an EUV resist underlayer film according to claim 1 or 2, wherein the reaction product contains structural units derived from the compound represented by formula (1) at a molar ratio of 50 mol% or more.

4. The composition for forming an EUV resist underlayer film according to claim 1 or 2, further comprising a crosslinking agent.

5. The composition for forming an EUV resist underlayer film according to claim 1 or 2, further comprising a crosslinking catalyst.

6. The composition for forming an EUV resist underlayer film according to claim 1 or 2, wherein the diepoxide is a compound containing a heterocycle.

7. An EUV resist underlayer film, characterized in that, It is a fired product of a coating film formed from the composition for forming an EUV resist underlayer film according to any one of claims 1 to 6.

8. A method for manufacturing a patterned substrate, comprising the following steps: a step of coating the composition for forming an EUV resist underlayer film according to any one of claims 1 to 6 on a semiconductor substrate and baking to form an EUV resist underlayer film; a step of coating an EUV resist on the EUV resist underlayer film and baking to form an EUV resist film; a step of exposing the semiconductor substrate covered with the EUV resist underlayer film and the EUV resist; and a step of developing the exposed EUV resist film to form a pattern.

9. A method for manufacturing a semiconductor device, characterized in that, Comprising the following steps: A step of forming an EUV resist underlayer film formed from the composition for forming an EUV resist underlayer film according to any one of claims 1 to 6 on a semiconductor substrate; A step of forming an EUV resist film on the EUV resist underlayer film; A step of forming an EUV resist pattern by irradiation of light or electron rays on the EUV resist film and subsequent development; A step of forming a patterned EUV resist underlayer film by etching the EUV resist underlayer film through the formed EUV resist pattern; and A step of processing the semiconductor substrate using the patterned EUV resist underlayer film.

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