Composition for forming an underlayer film for a resist, containing a blocked reaction product

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. The present invention relates to a composition for forming an underlayer film of a resist, which comprises a polymer having terminals blocked by a compound (A) and an organic solvent, and the polymer is a polymer derived from a compound (B) represented by the following formula (11) (in the formula (11), Y 1 represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted by a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group, and T 1 and T 2 represent an alkyl group having 1 to 10 carbon atoms, and n1 and n2 each independently represent an integer of 0 to 4).

Description

Technical Field

[0001] The present invention relates to a composition used in a lithography process in semiconductor manufacturing, particularly in the most advanced (ArF, EUV, EB, etc.) lithography processes. In addition, it relates to a method for manufacturing a substrate with a resist pattern using the above-mentioned underlayer film for a resist, and a method for manufacturing a semiconductor device. Background Art

[0002] Hitherto, in the manufacture of semiconductor devices, microfabrication has been carried out by lithography using a resist composition. The above-mentioned microfabrication is the following processing method: a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, and ultraviolet rays and other active rays are irradiated thereon through a mask pattern depicting a device pattern, followed by development, and the resulting photoresist pattern is used as a protective film to etch the substrate, thereby forming fine irregularities corresponding to the above-mentioned pattern on the substrate surface. In recent years, with the development of high integration of semiconductor devices, for the active rays used, 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 (extreme ultraviolet light, wavelength 13.5 nm) or EB (electron beam) has also been studied in the most advanced microfabrication. Along with this, the influence of the semiconductor substrate on the resist has become a major problem.

[0003] Therefore, in order to solve this problem, methods of providing an anti-reflection film (Bottom Anti-Reflective Coating: BARC) and an underlayer film for a resist between the resist and the semiconductor substrate have been widely studied. In Patent Document 1, a composition for forming an underlayer film for a resist used in a lithography process in semiconductor device manufacturing is disclosed, which contains a polymer having a repeating unit structure containing a polycyclic aliphatic ring in the main chain of the polymer. In Patent Document 2, a composition for forming an underlayer film for a lithography resist is disclosed, which contains a polymer having a specific structure at the end.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid-Open No. 2009-093162

[0007] Patent Document 2: International Publication No. 2013 / 141015 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] As the characteristics required for an underlayer film for a resist, for example, no mixing with the resist film formed thereon (insoluble in the resist solvent) and a dry etching rate faster than that of 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 and used in a manner thinner than in the past. When forming such a thin film, due to the influence of the substrate surface, the polymer used, etc., it is easy to generate pinholes, agglomeration, etc., and it is difficult to form a defect-free uniform film.

[0011] On the other hand, when forming a resist pattern, in the development process, sometimes the following method is adopted: using a solvent capable of dissolving the resist film, usually an organic solvent, to remove the unexposed portion of the resist film, and leaving the exposed portion of the resist film as a resist pattern. In such a negative development process, the improvement of the adhesion of the resist pattern has become a major issue.

[0012] In addition, it is necessary to suppress the deterioration of LWR (Line Width Roughness, the variation (roughness) of the line width) when forming a resist pattern, thereby forming 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 for a resist that solves the above problems and is capable of forming a desired resist pattern, and a method for forming a resist pattern using the composition for forming an underlayer film for a resist.

[0014] Means for solving the problems

[0015] The present invention includes the following.

[0016] [1] A composition for forming an underlayer film for a resist, which is a composition for forming an underlayer film for a resist containing a polymer having a terminal blocked by a compound (A) and an organic solvent, and the polymer is a polymer derived from a compound (B) represented by the following formula (11).

[0017]

[0018] (In formula (11),

[0019] Y 1 represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted by a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group,

[0020] T 1 and T 2 represent an alkyl group having 1 to 10 carbon atoms,

[0021] n1 and n2 each independently represent an integer of 0 to 4).

[0022] Preferably, it is a composition for forming an underlayer film of a resist, which is a composition for forming an underlayer film of a resist containing a polymer whose terminals are blocked by compound (A) and an organic solvent, and the polymer contains a repeating unit structure derived from compound (B) represented by the above formula (11).

[0023] [2] The composition for forming an underlayer film of a resist according to [1], wherein compound (A) contains an aliphatic ring which may be substituted with a substituent.

[0024] [3] The composition for forming an underlayer film of a resist according to [2], wherein the aliphatic ring is a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

[0025] [4] The composition for forming an underlayer film of a resist according to [2], wherein the aliphatic ring is a bicyclic ring or a tricyclic ring.

[0026] [5] The composition for forming an underlayer film of a resist according to any one of [2] to [4], wherein the substituent is selected from a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom, and a carboxyl group.

[0027] [6] The composition for forming an underlayer film of a resist according to [1], wherein compound (A) is represented by the following formula (1) or formula (2),

[0028]

[0029] (In formula (1) and formula (2), R1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogenated group or a hydroxyl group, R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogenated group or an ester group represented by -C(=O)O-X, X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogenated group, R4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms, R5 represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocyclic ring, t represents 0 or 1, and u represents 1 or 2.).

[0030] [7] The composition for forming an underlayer film of a resist according to any one of [1] to [6], wherein the polymer contains a repeating unit structure derived from compound (B) and compound (C) capable of reacting with compound (B), and compound (C) has a heterocyclic structure.

[0031] Preferably, it is a composition for forming an underlayer film for a resist according to any one of [1] to [6], and the polymer contains a repeating unit structure derived from the compound (B) and a compound (C) capable of reacting with the compound (B), and the compound (C) has a heterocyclic structure.

[0032] [8] The composition for forming an underlayer film for a resist according to any one of [1] to [7], wherein the Y 1 is a sulfonyl group.

[0033] [9] The composition for forming an underlayer film for a resist according to any one of [1] to [8], which further contains an acid generator.

[0034]

[10] The composition for forming an underlayer film for a resist according to any one of [1] to [9], which further contains a crosslinking agent.

[0035]

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

[10] .

[0036]

[12] A method for manufacturing a patterned substrate, which includes: a step of coating the composition for forming an underlayer film for a resist according to any one of [1] to

[10] on a semiconductor substrate and baking to form an underlayer film for a resist; a step of coating a resist on the underlayer film for a resist and baking to form a resist film; a step of exposing the semiconductor substrate covered with the underlayer film for a resist and the resist; and a step of developing the exposed resist film to form a pattern.

[0037]

[13] A method for manufacturing a semiconductor device, characterized by including:

[0038] a step of forming an underlayer film for a resist formed from the composition for forming an underlayer film for a resist according to any one of [1] to

[10] on a semiconductor substrate;

[0039] a step of forming a resist film on the underlayer film for a resist;

[0040] a step of forming a resist pattern by irradiation of light or electron rays on the resist film and subsequent development;

[0041] a step of forming a patterned underlayer film for a resist by etching the underlayer film for a resist through the formed resist pattern; and

[0042] a step of processing the semiconductor substrate using the patterned underlayer film for a resist.

[0043] Advantages of the Invention

[0044] The underlayer resist film formed from the composition for forming an underlayer resist film containing a polymer whose ends are blocked by a compound exhibits excellent resistance to the organic solvents used in the photoresist formed on top of this underlayer film. Also, even in the case of an extremely thin film (film thickness of 10 nm or less), an underlayer resist film with good film thickness uniformity can be formed. In addition, when forming a resist pattern using the composition for forming an underlayer resist film of the present invention, the limit resolution size at which the developed resist pattern collapses is observed to be smaller compared to conventional underlayer resist films, and a finer resist pattern can be formed. Further, an effect can be achieved where the range of resist pattern sizes showing good patterns is increased compared to the prior art. Detailed Description

[0045] <Composition for Forming an Underlayer Resist Film>

[0046] The composition for forming an underlayer resist film of the present invention contains a polymer whose ends are blocked by a compound (A) and an organic solvent.

[0047] <Polymer>

[0048] The polymer of the present invention is a polymer derived from a compound (B) represented by the following formula (11), and preferably contains, as a repeating unit structure, the reaction product of the above compound (B) and a compound (C) capable of reacting therewith.

[0049]

[0050] (In formula (11),

[0051] Y 1 represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted by a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group,

[0052] T 1 and T 2 represent an alkyl group having 1 to 10 carbon atoms,

[0053] n1 and n2 each independently represent an integer of 0 to 4)

[0054] The above Y 1 is preferably a sulfonyl group.

[0055] Examples of the aryl group having 6 to 40 carbon atoms described above include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

[0056] Examples of the alkylene group having 1 to 10 carbon atoms described above include methylene, ethylene, n-propylene, isopropylidene, cyclopropylidene, n-butylene, isobutylene, sec-butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylidene, 2-methyl-cyclopropylidene, 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-cyclopropylidene, 2,3-dimethyl-cyclopropylidene, 1-ethyl-cyclopropylidene, 2-ethyl-cyclopropylidene, 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-cyclopropylidene, 2-n-propyl-cyclopropylidene, 1-isopropyl-cyclopropylidene, 2-isopropyl-cyclopropylidene, 1,2,2-trimethyl-cyclopropylidene, 1,2,3-trimethyl-cyclopropylidene, 2,2,3-trimethyl-cyclopropylidene, 1-ethyl-2-methyl-cyclopropylidene, 2-ethyl-1-methyl-cyclopropylidene, 2-ethyl-2-methyl-cyclopropylidene, 2-ethyl-3-methyl-cyclopropylidene, n-heptylene, n-octylene, n-nonylene, or n-decylene.

[0057] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 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-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 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-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, and decyl. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and it is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and more preferably methyl or ethyl.

[0058] The above polymer preferably has a heterocyclic structure. That is, it is preferred that the compound (C) capable of reacting described below contains a heterocyclic structure.

[0059] Examples of the above heterocyclic structure include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazinone, triazinedione, and triazinetrione, and the heterocyclic structures represented by (10-h) to (10-k) listed as specific examples of the following compound (C). Among them, triazinetrione or the heterocyclic structure described in the following formula (10-k) is preferred.

[0060] <Compound (C) capable of reacting with compound (B)>

[0061] As the above-mentioned compound (C) capable of reacting, there is no particular limitation as long as it is a compound (C) having a substituent capable of reacting with the hydroxyl group of compound (B), but a compound containing two epoxy groups is preferred. Specific examples of the compound (C) capable of reacting are the compounds described below.

[0062]

[0063] The weight-average molecular weight of the above polymer is preferably 500 to 50,000, more preferably 1,000 to 30,000. The above weight-average molecular weight can be measured by, for example, gel permeation chromatography described in the examples.

[0064] The proportion of the above polymer contained in the entire resist underlayer film-forming composition of the present invention is usually 0.05% by mass to 3.0% by mass, 0.08% by mass to 2.0% by mass, and 0.1% by mass to 1.0% by mass.

[0065] Examples of the organic solvent contained in the resist underlayer film-forming composition 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.

[0066] 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.

[0067] <Compound (A)[1]>

[0068] The above compound (A) preferably contains an aliphatic ring which may be substituted by a substituent.

[0069] The above aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. Examples of the monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, tricyclo[3.2.1.0 2,7 octane, spiro[3,4]octane, norbornane, norbornene, tricyclo[3.3.1.1 3,7 decane (adamantane), etc.

[0070] The above polycyclic aliphatic ring is preferably a bicyclic ring or a tricyclic ring.

[0071] Examples of the above bicyclic ring include norbornane, norbornene, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, spiro[3,4]octane, etc.

[0072] Examples of the above tricyclic ring include tricyclo[3.2.1.0 2,7 octane, tricyclo[3.3.1.1 3,7 decane (adamantane).

[0073] The above aliphatic ring which may be substituted by a substituent means that one or more hydrogen atoms of the aliphatic ring may be substituted by the substituents described below.

[0074] Preferably, the above substituents are selected from a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom, and a carboxyl group.

[0075] Examples of the alkoxy group having 1 to 20 carbon atoms described above include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, cyclopentyloxy, cyclohexyloxy, norbornyloxy, adamantyloxy, adamantanemethyloxy, adamantylethyloxy, tetracyclodecyloxy, tricyclodecyloxy.

[0076] The above aliphatic ring preferably has at least 1 unsaturated bond (e.g., double bond, triple bond). The above aliphatic ring preferably has 1 to 3 unsaturated bonds. The above aliphatic ring preferably has 1 or 2 unsaturated bonds. The above unsaturated bond is preferably a double bond.

[0077] As specific examples of the compound containing the above aliphatic ring which may be substituted with a substituent, the compounds described below can be mentioned. Compounds in which the carboxyl group in the following specific examples is replaced with a hydroxyl group, an amino group or a thiol group can also be mentioned as specific examples.

[0078]

[0079]

[0080] When the compound described above still has a carboxyl group after reacting at the polymer terminal, the carboxyl group can react with an alcohol compound. The above alcohol compound can be an organic solvent contained in the above composition for forming an underlayer film of a resist.

[0081] As specific examples of the above alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methanol, ethanol, 1-propanol and 2-propanol can be mentioned.

[0082] <Compound (A)[2])>

[0083] The above compound (A) is preferably represented by the following formula (1) and formula (2).

[0084]

[0085] (In Formulas (1) and (2), R1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogenated group or a hydroxyl group; R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogenated group or an ester group represented by -C(=O)O-X; X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogenated group; R4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms; R5 represents a divalent organic group having 1 to 8 carbon atoms; A represents an aromatic ring or an aromatic heterocyclic ring; t represents 0 or 1; u represents 1 or 2.)

[0086] Regarding the content of the above Formulas (1) and (2), all the disclosure contents described in International Publication No. 2015 / 163195 are incorporated herein by reference in their entirety into this application.

[0087] The above polymer terminal structures represented by the above Formulas (1) and (2) can be produced by the reaction of the above polymer with a compound represented by the following Formula (1a) and / or a compound represented by the following Formula (2a).

[0088]

[0089] (The meanings of the symbols in the above Formulas (1a) and (2a) are as described in the above Formulas (1) and (2).)

[0090] As the compound represented by the above Formula (1a), compounds represented by the following formulas can be exemplified.

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] As the compound represented by the above Formula (2a), compounds represented by the following formulas can be exemplified.

[0097]

[0098] When the compound described above still has a carboxyl group after the reaction at the polymer terminal, the carboxyl group can react with an alcohol compound. The above alcohol compound can be an organic solvent contained in the above composition for forming an underlayer film of a resist.

[0099] As specific examples of the above alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methanol, ethanol, 1-propanol, and 2-propanol can be mentioned.

[0100] <Acid generator>

[0101] As the acid generator that can be included as an optional component in the composition for forming an anti-reflective film of the present invention, any acid generator such as a thermal acid generator or a photoacid generator can be used, but a thermal acid generator is preferably used. As the thermal acid generator, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonate), pyridinium p-hydroxybenzenesulfonate (pyridinium p-phenolsulfonate), pyridinium trifluoromethanesulfonate, 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, N-methylmorpholine-5-sulfosalicylic acid and other sulfonic acid compounds and carboxylic acid compounds can be mentioned.

[0102] As the above photoacid generator, onium salt compounds, sulfimide compounds, disulfonyldiazomethane compounds, etc. can be mentioned.

[0103] As the onium salt compound, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate can be mentioned.

[0104] As the sulfimide compound, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenedicarboximide, etc. can be mentioned.

[0105] As the disulfonyldiazomethane compound, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane can be mentioned.

[0106] The above acid generator can be used alone, or two or more thereof can be used in combination.

[0107] In the case of using the above acid generator, the content ratio of the acid generator relative to the following crosslinking agent is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass.

[0108] <Crosslinking agent>

[0109] Examples of the crosslinking agent that can be included as an optional component in the composition for forming an anti-reflective film of the present invention include, for example, 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, and 1,1,3,3-tetra(methoxymethyl)urea.

[0110] In addition, the crosslinking agent of the present application may also be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom, as described in International Publication No. 2017 / 187969.

[0111]

[0112] (In formula (1d), R1 represents a methyl group or an ethyl group.)

[0113] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0114]

[0115] (In formula (1E), the 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.)

[0116] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formula (1E-1) to formula (1E-6).

[0117]

[0118] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom, and at least one compound represented by the following formula (3d).

[0119]

[0120] (In formula (3d), R1 represents methyl or ethyl, and in formula (2d), R4 represents an alkyl group having 1 to 4 carbon atoms.)

[0121] The glycoluril derivative represented by the above formula (1E) can be obtained by reacting the glycoluril derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0122] Examples of the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) in one molecule include glycoluril derivatives represented by the following formula (2E).

[0123]

[0124] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0125] Examples of the glycoluril derivative represented by the above formula (2E) include compounds represented by the following formulae (2E-1) to (2E-4). In addition, examples of the compound represented by the above formula (3d) include compounds represented by the following formulae (3d-1) and (3d-2).

[0126]

[0127] Regarding the content related to the nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0128] When using the above crosslinking agent, the content ratio of the crosslinking agent relative to the above reaction product is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass.

[0129] <Other components>

[0130] 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 against surface unevenness, a surfactant can 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 solid components of the composition for forming an underlayer film of a resist of the present invention. These surfactants can be added alone, or can be added in combination of two or more kinds.

[0131] The composition for forming an underlayer film of a resist of the present invention is preferably a composition for forming an underlayer film of an electron beam (EB) resist or a composition for forming an underlayer film of an EUV resist, which is used in an electron beam lithography process and an EUV exposure process, and is more preferably a composition for forming an underlayer film of an EUV resist.

[0132] <Underlayer film of resist>

[0133] The underlayer film of a resist according to the present invention can be manufactured by coating the above-described composition for forming an underlayer film of a resist on a semiconductor substrate and firing it.

[0134] The underlayer film of a resist according to the present invention is preferably an underlayer film of an electron beam resist or an underlayer film of an EUV resist.

[0135] Examples of the semiconductor substrate coated with the composition for forming the resist underlayer film 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.

[0136] In the case of using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film can be formed by, for example, ALD (Atomic Layer Deposition) method, CVD (Chemical Vapor Deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). Examples of the inorganic film include polycrystalline silicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium oxynitride film, tungsten film, gallium nitride film, and gallium arsenide film.

[0137] On such a semiconductor substrate, the composition for forming the resist underlayer film 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 a resist underlayer film. As the baking conditions, appropriate selection can be 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.

[0138] The film thickness of the formed 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), or 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 resist underlayer film may decompose due to heat.

[0139] <Method for manufacturing a patterned substrate, method for manufacturing a semiconductor device>

[0140] The method for manufacturing a patterned substrate goes through the following processes. Generally, it is manufactured by forming a photoresist layer on an underlayer resist film. As the photoresist formed by coating and baking on the underlayer resist film using a method known per se, any photoresist that is sensitive to light used for exposure can be used, and there is no particular limitation. Any photoresist among negative photoresists and positive photoresists can be used. There are the following photoresists: a positive photoresist composed of a novolak resin and 1,2-naphthoquinone diazide sulfonate; a chemically amplified photoresist composed of a binder having a group that decomposes under the action of an acid to increase the alkali dissolution rate and a photoacid generator; a chemically amplified photoresist composed of a low molecular weight compound that decomposes under the action of an acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; and a chemically amplified photoresist composed of a binder having a group that decomposes under the action of an acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes under the action of an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; a resist containing a metal element, etc. Examples include products with the trade names V146G manufactured by JSR Corporation, APEX-E manufactured by Shipley Company, PAR710 manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, for example, fluorine atom-containing polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited. In addition, it can be a so-called metal-containing resist (metal resist).As a specific example, it is possible to use resist compositions, radiation-sensitive resin compositions, high-resolution patterning compositions based on organometallic solutions, and the like, such as those 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., but is not limited thereto.

[0141] Examples of the resist composition include, for example, the following resist compositions.

[0142] A chemically amplified resin composition containing resin A and a compound represented by the general formula (1), wherein 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 under the action of an acid.

[0143]

[0144] In the general formula (1), m represents an integer of 1 to 6.

[0145] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0146] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0147] L2 represents an alkylene group which may have a substituent or a single bond.

[0148] W1 represents a cyclic organic group which may have a substituent.

[0149] M + represents a cation.

[0150] 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.

[0151] A radiation-sensitive resin composition containing: a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2) and containing an acid-dissociable group; and an acid generator.

[0152]

[0153] (In the formula (1), 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 thioalkyl 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.

[0154] In the formula (2), R 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.)

[0155] A resist composition containing a resin (A1); and an acid generator, wherein the resin (A1) includes a structural unit having a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit having an acid-labile group.

[0156]

[0157] [In formula (II),

[0158] 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, and X 1 represents a single bond, -CO-O-*, or -CO-NR 4 -*, where * represents a bonding site to -Ar, and 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 hydroxyl group and a carboxyl group.]

[0159] A resist composition which generates an acid upon exposure and whose solubility in a developer changes under the action of the acid, characterized in that

[0160] it contains a substrate component (A) whose solubility in a developer changes under the action of an acid and a fluorine additive component (F) which shows decomposability with respect to an alkali developer,

[0161] The above-mentioned 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).

[0162]

[0163] [In formula (f2-r-1), Rf 21 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n” is an integer of 0 to 2. * is a bonding site.]

[0164] A resist composition, wherein the above-mentioned 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).

[0165]

[0166] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable 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. Each R 2 is independently an organic group having a fluorine atom.]

[0167] Examples of the resist material include the following resist materials.

[0168] A resist material containing a polymer having a repeating unit represented by the following formula (a1) or (a2).

[0169]

[0170] (In formulas (a1) and (a2), R A is a hydrogen atom or a methyl group. X 1 is a single bond or an ester group. X 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a part of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring. In addition, at least one hydrogen atom contained in X 2 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, and 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, but at least one of them is a fluorine atom or a trifluoromethyl group. In addition, 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, and 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, and 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. In addition, R 1 and R 2 may bond to form a ring together with the sulfur atom to which they are bonded.)

[0171] A resist material comprising a base resin, the base resin comprising a polymer containing a repeating unit represented by the following formula (a).

[0172]

[0173] (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 an ester group or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain 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.)

[0174] Examples of the resist film include the following resist films.

[0175] (i) A resist film comprising a base resin, the 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 the polymer main chain upon exposure.

[0176]

[0177] (In formulas (a1) and (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 or 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.)

[0178] Examples of the coating solution include the following.

[0179] As a resist composition containing a metal, for example, a coating comprising a metal oxo-hydroxo network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0180] An inorganic oxo / hydroxy-based composition.

[0181] A coating solution comprising: an organic solvent; a first organometallic composition; and a hydrolyzable metal compound, the first organometallic composition being 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; the hydrolyzable metal compound being represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0182] 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), the solution containing from about 0.0025 M to about 1.5 M of tin, and R being an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to tin at a secondary or tertiary carbon atom).

[0183] An aqueous precursor solution for inorganic pattern formation formed by mixing water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group).

[0184] Exposure is performed through a mask (reticle) for forming a prescribed pattern. For example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. However, the composition for forming an underlayer film of a resist of the present invention is preferably applied to EUV (extreme ultraviolet) exposure applications. In development, an alkali developer can be used, and it can be appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As the alkali developer, for example, inorganic alkalis 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 as aqueous solutions of alkalis. In addition, an appropriate amount of alcohols such as isopropanol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the above alkalis for use. Among them, the preferred developer is a quaternary ammonium salt, and more preferably tetramethylammonium hydroxide and choline. In addition, a surfactant or the like can be added to these developers. The following method can also be adopted: Instead of an alkali developer, development is performed using an organic solvent such as butyl acetate to develop the portion where the alkali dissolution rate of the photoresist is not increased. Through the above process, a substrate on which the above resist has been patterned can be manufactured.

[0185] Next, the formed resist pattern is used as a mask, and the underlayer film of the resist is dry-etched. 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 a process of processing the substrate by a method known per se (dry etching method, etc.), a semiconductor device can be manufactured.

[0186] Examples

[0187] Hereinafter, examples and comparative examples are given to more specifically illustrate the present invention, but the present invention is not limited to the following examples.

[0188] The weight average molecular weights of the polymers shown in Synthesis Example 1 to Synthesis Example 2 and Comparative Synthesis Example 1 in the following description of this specification are measurement results obtained by gel permeation chromatography (hereinafter, simply referred to as GPC). In the measurement, a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions and the like are as described below.

[0189] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.)

[0190] Column temperature: 40°C

[0191] Solvent: N,N-dimethylformamide (DMF)

[0192] Flow rate: 0.6 ml / min

[0193] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0194] <Synthesis Example 1>

[0195] 4.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a raw material for Polymer 1, 3.72 g of bis(4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.70 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.13 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.36 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 26.76 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a solution of Polymer 1. GPC analysis was performed. As a result, the weight-average molecular weight of the obtained Polymer 1 in terms of standard polystyrene was 7600, and the dispersity was 3.2. The structure present in Polymer 1 is shown in the following formula.

[0196]

[0197] <Synthesis Example 2>

[0198] 4.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a raw material for Polymer 2, 3.72 g of bis(4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.77 g of 1-hydroxyadamantane carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.13 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.36 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 26.96 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a solution of Polymer 2. GPC analysis was performed. As a result, the weight-average molecular weight of the obtained Polymer 2 in terms of standard polystyrene was 7400, and the dispersity was 3.4. The structure present in Polymer 2 is shown in the following formula.

[0199]

[0200] <Synthesis Example 3>

[0201] 4.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a raw material for Polymer 3, 3.72 g of bis(4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.84 g of 3-hydroxy-1-adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.13 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 27.17 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a solution of Polymer 3. GPC analysis was performed, and as a result, the obtained Polymer 3 had a weight-average molecular weight of 7400 and a dispersity of 3.2 in terms of standard polystyrene conversion. The structure present in Polymer 3 is shown in the following formula.

[0202]

[0203] <Synthesis Example 4>

[0204] 4.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a raw material for Polymer 4, 3.72 g of bis(4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.86 g of 4-methylsulfonylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.13 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 36.29 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a solution of Polymer 4. GPC analysis was performed, and as a result, the obtained Polymer 4 had a weight-average molecular weight of 6200 and a dispersity of 3.9 in terms of standard polystyrene conversion. The structure present in Polymer 4 is shown in the following formula.

[0205]

[0206] <Comparative Synthesis Example 1>

[0207] 3.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 3.94 g of bis(4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.10 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 21.93 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a solution of Comparative Polymer 1. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Comparative Polymer 1 in terms of standard polystyrene was 6,400, and the dispersity was 4.6. The structure present in Comparative Polymer 1 is shown in the following formula.

[0208]

[0209] (Preparation of Antireflective Underlayer Film)

[0210] (Examples)

[0211] The polymers, crosslinking agents, curing catalysts (acid generators), and solvents obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 above were mixed in the proportions shown in Tables 1 and 2, and filtered using a 0.1-μm fluororesin filter, whereby solutions of the compositions for forming antireflective underlayer films were respectively prepared.

[0212] In Tables 1 and 2, tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.) is abbreviated as PL-LI, Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- is abbreviated as PGME-PL, pyridinium p-hydroxybenzenesulfonate is abbreviated as PyPSA, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. Each addition amount is shown in parts by mass.

[0213] Table 1

[0214]

[0215] Table 2

[0216]

[0217] (Dissolution Test in Photoresist Solvent)

[0218] The composition for forming an underlayer film of a resist according to Examples 1 to 8 and Comparative Example 1 was respectively coated onto a silicon wafer using a spinner. On a hot plate, the silicon wafer was baked at 205 °C for 60 seconds to obtain a film with a film thickness of 5 nm. These underlayer films of the resist were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is a solvent for a photoresist. When the film thickness change was as follows, it was marked as good, and when the film thickness change was above, it was marked as bad. The results are shown in Table 3.

[0219] (Film-forming property test)

[0220] The composition for forming an underlayer film of a resist according to Examples 1 to 8 and Comparative Example 1 was respectively coated onto a silicon wafer using a spinner. On a hot plate, the silicon wafer was baked at 205 °C for 60 seconds to obtain films with film thicknesses of 5 nm and 3.5 nm. For these underlayer films of the resist, the surface roughness (Sa) was measured using an atomic force microscope (AFM). When it was good compared to Comparative Example 1, it was marked as good, and when it deteriorated compared to Comparative Example 1, it was marked as bad. The results are shown in Table 3.

[0221] Table 3

[0222]

[0223] (Evaluation of resist patterning)

[0224] [Formation test of resist pattern using an electron beam lithography apparatus]

[0225] Using a spinner, the composition for forming an underlayer film of a resist was respectively coated onto a silicon wafer. On a hot plate, the silicon wafer was baked at 205 °C for 60 seconds to obtain an underlayer film of a resist with a film thickness of 5 nm. An EUV positive resist solution was spin-coated onto this underlayer film of the resist and heated at 110 °C for 60 seconds to form an EUV resist film. For this resist film, using an electron beam lithography apparatus (ELS-G130), exposure was performed under specified conditions. After exposure, baking (PEB) was performed at 90 °C for 60 seconds, and it was cooled to room temperature on a cooling plate. A 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) was used as a developer for the photoresist, and spin-on immersion development was performed for 60 seconds. A resist pattern with a line size of 15 nm to 27 nm was formed. In the measurement of the length of the resist pattern, a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used.

[0226] For the photoresist pattern obtained as described above, evaluation was carried out based on the ability to form a 22-nm line and space (L / S). In all cases of Example 1, Example 3, and Comparative Example 1, formation of a 22-nm L / S pattern was confirmed. In addition, the amount of charge for forming a 22-nm line / 44-nm space (line and space (L / S = 1 / 1)) was taken as the most suitable irradiation energy, and the irradiation energy (μC / cm 2 ) value was smaller, indicating higher sensitivity of the resist. The results of Example 1 and 3 showed values lower than those of Comparative Example 1, indicating an improvement in sensitivity. In addition, when observed from the upper part of the pattern, the minimum CD size at which collapse was not observed inside the lens of the resist pattern was confirmed. The smaller this value, the better the adhesion to the resist. The results of Example 1 and 3 had smaller minimum CD size values compared to Comparative Example 1, indicating good adhesion to the resist.

[0227] Table 4

[0228]

[0229] Industrial applicability

[0230] The composition for forming an underlayer film for a resist according to the present invention can provide a composition for forming an underlayer film for a resist capable of forming a desired resist pattern, a method for manufacturing a substrate with a resist pattern using the composition for forming an underlayer film for a resist, and a method for manufacturing a semiconductor device.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer having its terminal blocked by a compound (A) and an organic solvent, wherein the polymer is a polymer having a repeating unit structure derived from a compound (B) represented by the following formula (11) and a compound (C) capable of reacting with the compound (B), In formula (11), Y 1 represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms or a sulfonyl group which may be substituted by a halogen atom or an aryl group having 6 to 40 carbon atoms, T 1 and T 2 represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 each independently represent an integer of 0 to 4, The compound (C) is a compound containing two epoxy groups, The compound (A) is selected from the following compounds, and compounds in which the carboxyl group of the following compounds is replaced with a hydroxyl group, an amino group or a thiol group, 2 . The resist underlayer film-forming composition according to claim 1 , wherein the compound (C) has a heterocyclic structure.

3. The composition for forming an underlayer film of a resist according to claim 1 or 2, wherein the Y 1 is a sulfonyl group. 4 . The resist underlayer film forming composition according to claim 1 , further comprising an acid generator. 5 . The resist underlayer film-forming composition according to claim 1 , further comprising a crosslinking agent.

6. A resist underlayer film, characterized in that, This is a fired product of a coating film formed from the resist underlayer film forming composition according to any one of claims 1 to 5.

7. A method for manufacturing a patterned substrate, comprising: A step of coating the resist underlayer film-forming composition according to any one of claims 1 to 5 on a semiconductor substrate and baking the composition to form a resist underlayer film; A step of coating a resist on the resist underlayer film and baking the resist to form a resist film; A step of exposing the semiconductor substrate covered with the resist underlayer film and the resist; and a step of developing the exposed resist film to perform patterning.

8. A method of manufacturing a semiconductor device, characterized in that, include: A step of forming a resist underlayer film formed from the resist underlayer film-forming composition according to any one of claims 1 to 5 on a semiconductor substrate; forming a resist film on the resist underlayer film; A step of forming a resist pattern by irradiating a resist film with light or electron beams and then developing the resist film; a step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; and A step of processing a semiconductor substrate using the patterned resist underlayer film.

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