Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film, which contains (A) a polymer having an organic boric acid structure and (B) a solvent.

Description

Technical Field

[0001] The present invention relates to a composition for forming an underlayer film for a resist, an underlayer film for a resist, a laminate, a method for manufacturing a semiconductor device, and a method for forming a pattern. Background Art

[0002] In the manufacturing of semiconductor devices, fine processing has been performed 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 thereon through a mask pattern depicting a device pattern, developing, and etching the substrate using the obtained photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the above-mentioned photoresist pattern on the substrate surface. In recent years, with the progress of high integration of semiconductor devices, in addition to the i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm) that have been used in the past, the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) has been studied in the most advanced fine processing. Along with this, poor resist pattern formation caused by the influence from a semiconductor substrate or the like has become a major problem. Therefore, in order to solve this problem, a method of providing an underlayer film for a resist between the resist and the semiconductor substrate has been widely studied.

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

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2006 / 003850

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-526270

[0008] Patent Document 3: International Publication No. 2020 / 111068 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] As characteristics required for an underlayer film for a resist, for example, non-mixing with the resist film formed on the upper layer (insoluble in the resist solvent) and the ability to form a resist pattern with high sensitivity can be cited.

[0011] The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition for forming an underlayer film for a resist, an underlayer film for a resist, a laminate, a method for manufacturing a semiconductor element, and a method for forming a pattern, which can form a resist pattern with high sensitivity.

[0012] Means for Solving the Problems

[0013] The present inventors conducted intensive studies to solve the above problems, and as a result, found that the above problems can be solved, and completed the present invention having the following gist.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A composition for forming an underlayer film for a resist, comprising: a polymer (A) having an organic boronic acid structure, and a solvent (B).

[0016] [2] The composition for forming an underlayer film for a resist according to [1], wherein the organic boronic acid structure is an aryl boronic acid structure.

[0017] [3] The composition for forming an underlayer film for a resist according to [1] or [2], wherein the solvent (B) includes at least one selected from alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0018] [4] The composition for forming an underlayer film for a resist according to any one of [1] to [3], further comprising a crosslinking agent (C).

[0019] [5] The composition for forming an underlayer film for a resist according to [4], wherein the crosslinking agent (C) is at least one selected from aminoplast crosslinking agents and phenolic plastic crosslinking agents.

[0020] [6] The composition for forming an underlayer film for a resist according to any one of [1] to [5], further comprising a curing catalyst (D).

[0021] [7] An underlayer film for a resist, which is a cured product of the composition for forming an underlayer film for a resist according to any one of [1] to [6].

[0022] [8] A laminate, comprising

[0023] a semiconductor substrate, and

[0024] the underlayer film for a resist according to [7].

[0025] [9] A method for manufacturing a semiconductor element, comprising the following steps:

[0026] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as described in any one of [1] to [6]; and

[0027] A step of forming a resist film on the resist underlayer film.

[0028]

[10] A pattern forming method comprising the following steps:

[0029] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to [6];

[0030] forming a resist film on the resist underlayer film;

[0031] a step of irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and

[0032] A step of etching the resist underlayer film using the resist pattern as a mask.

[0033] Effects of the Invention

[0034] According to the present invention, there can be provided a resist underlayer film forming composition capable of forming a resist underlayer film capable of forming a resist pattern with high sensitivity, and a resist underlayer film, a laminate, a semiconductor element manufacturing method and a pattern forming method using the resist underlayer film forming composition. DETAILED DESCRIPTION

[0035] (Resist underlayer film forming composition)

[0036] The resist underlayer film-forming composition of the present invention contains a polymer (A) and a solvent (B).

[0037] The resist underlayer film-forming composition may contain a crosslinking agent (C), a curing catalyst (D), and the like.

[0038] The polymer (A) has an organic boronic acid structure.

[0039] When the polymer (A) has an organic boronic acid structure, a resist pattern can be formed with high sensitivity.

[0040] <Polymer (A)>

[0041] The polymer (A) has an organic boronic acid structure.

[0042] The organic boronic acid structure is, for example, a structure represented by the following formula (B1).

[0043]

[0044] (In formula (B1), R a and R b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. In addition, R a and R b may together form a ring structure having 3 to 6 carbon atoms.

[0045] R 1 represents an organic group having a valence of 2 or more.)

[0046] R 1 is, for example, divalent or trivalent.

[0047] When R 1 is divalent, formula (B1) is represented by the following formula (B1-1).

[0048] When R 1 is trivalent, formula (B1) is represented by the following formula (B1-2).

[0049]

[0050] (In formula (B1-1) and formula (B1-2), R a and R b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. In addition, R a and R b may together form a ring structure having 3 to 6 carbon atoms.

[0051] R 1a represents a divalent organic group.

[0052] R 1b represents a trivalent organic group.

[0053] * represents a bonding site.)

[0054] As for the number of carbon atoms of R 1 , R 1a and R 1b , there is no particular limitation, but it is preferably 1 to 10.

[0055] R 1 , R 1a and R 1b may also have, for example, a heteroatom. Examples of the heteroatom include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0056] R 1 , R 1a and R 1b are, for example, hydrocarbon groups, and preferably hydrocarbon groups having 1 to 10 carbon atoms.

[0057] From the viewpoint of suitably obtaining the effects of the present invention, the organic boronic acid structure is preferably an aryl boronic acid structure.

[0058] The aryl boronic acid structure refers to a structure among organic boronic acid structures that has an aromatic ring bonded to B (boron).

[0059] The so-called aryl boronic acid structure means, for example, in formula (B1), when R 1 is a divalent or higher organic group having an aromatic ring bonded to B (boron), the structure represented by formula (B1).

[0060] Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a benzene ring. Examples of the aromatic heterocyclic ring include a pyridine ring.

[0061] As R 1 , from the viewpoint of suitably obtaining the effects of the present invention, it is preferably a group in which two or more hydrogen atoms have been removed from the benzene ring.

[0062] As R 1a , from the viewpoint of suitably obtaining the effects of the present invention, it is preferably a divalent group (phenylene group) in which two hydrogen atoms have been removed from the benzene ring.

[0063] As R 1b , from the viewpoint of suitably obtaining the effects of the present invention, it is preferably a trivalent group in which three hydrogen atoms have been removed from the benzene ring.

[0064] Examples of the organic boronic acid structure include the following structures.

[0065]

[0066] (In the formula, * represents a bonding site.)

[0067] Polymer (A) has, for example, at least one or more unit structures, and at least one of the unit structures has an organic boronic acid structure.

[0068] Polymer (A) is, for example, an isocyanuric acid-based polymer. The so-called isocyanuric acid-based polymer refers to a polymer having the following isocyanuric acid skeleton.

[0069]

[0070] (In the formula, * represents a bonding site.)

[0071] It should be noted that one of the bonding sites indicated by * may also be bonded to a hydrogen atom.

[0072] In addition, the polymer (A) is, for example, a polyester-based polymer. The so-called polyester-based polymer refers to a polymer having at least an ester bond in the main chain. The ester bond in the polyester-based polymer is formed, for example, by the reaction of a -CO-X group (X represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms) with a hydroxyl group or an epoxy group.

[0073] It should be noted that in the case where a certain polymer has an isocyanuric acid skeleton and an ester bond in the main chain, the polymer is an isocyanuric acid-based polymer and is also a polyester-based polymer.

[0074] In addition, the polymer (A) is, for example, a vinyl-based polymer. The vinyl-based polymer is, for example, a polymer formed by the polymerization of polymerizable unsaturated bonds of a compound having a group with a polymerizable unsaturated bond. The vinyl-based polymer can be a homopolymer or a copolymer. Examples of the group with a polymerizable unsaturated bond include, for example, a (meth)acryloyl group, a vinylaryl group (for example, a styryl group), a vinyloxy group, an allyl group, etc.

[0075] The polymer (A) is, for example, a polymer having a hydroxyl group in the unit structure. The hydroxyl group is, for example, a hydroxyl group bonded to a secondary carbon atom.

[0076] The polymer (A) is not, for example, a polymer having both an acetal structure and an amide bond.

[0077] In addition, the polymer (A) is not, for example, a polymer having an acetal structure.

[0078] The so-called acetal structure refers to a structure in which the same carbon has two ether bonds.

[0079] The acetal structure is, for example, an acetal structure that protects two adjacent hydroxyl groups of an aromatic group.

[0080] The polymer (A) is not, for example, a polymer having both a structural unit containing an alicyclic structure and a functional group bonded to a group containing a silicon atom.

[0081] In addition, the polymer (A) is not, for example, a polymer having both a structural unit containing an alicyclic structure and a group containing a hydroxyl boron bonded to a group containing a silicon atom.

[0082] In addition, the polymer (A) is not, for example, a polymer having a group containing a hydroxyl boron bonded to a group containing a silicon atom.

[0083] Examples of the group containing a hydroxyl boron include, for example, -B(OH)2, -B(R)(OH) (R represents a hydrocarbon group).

[0084] <<Vinyl-based polymer (A1)>>

[0085] The case where the polymer (A) is a vinyl polymer (A1) will be described.

[0086] The vinyl polymer (A1) has, for example, a unit structure represented by the following formula (A1-1).

[0087]

[0088] (In formula (A1-1), R 11 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0089] L 1 represents a single bond or a linking group.

[0090] L 2 represents a single bond or a divalent organic group.

[0091] R a and R b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. Further, R a and R b may together form a ring structure having 3 to 6 carbon atoms.)

[0092] 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-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, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, cycloheptyl, norbornyl, n-octyl, cyclooctyl, n-nonyl, isobornyl, tricyclononyl, n-decyl, adamantyl, tricyclodecyl, etc. Among them, methyl is preferred.

[0093] Examples of the linking group in L 1 include, for example, an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-), an alkylene group having 1 to 6 carbon atoms, a -R-O- group (R represents an alkylene group having 1 to 6 carbon atoms), etc.

[0094] For example, in the vinyl-based polymer (A1), the organic boric acid structure is bonded to the main chain of the vinyl-based polymer (A1) via a linking group of a structure obtained by reacting an epoxy group with a nucleophilic functional group.

[0095] As the nucleophilic functional group, for example, one or more selected from a carboxyl group, a hydroxyl group, an amino group, and a thiol group can be mentioned. The hydroxyl group may be a phenolic hydroxyl group or may not be a phenolic hydroxyl group.

[0096] If the epoxy group reacts with the carboxyl group, it reacts as follows to form the following structure (S1).

[0097]

[0098] (In the formula, * represents a bonding site.)

[0099] In addition, for example, in the vinyl polymer (A1), the organoboric acid structure is bonded to the main chain of the vinyl polymer (A1) via a linking group having a structure obtained by reacting an isocyanate group with a nucleophilic functional group. In this case, as the nucleophilic functional group, for example, one or more selected from a hydroxyl group, an amino group, and a thiol group can be mentioned. The hydroxyl group may be a phenolic hydroxyl group or may not be a phenolic hydroxyl group.

[0100] As L 1 , for example, the following linking groups (L1-1) to (L1-9) can be mentioned.

[0101]

[0102] (In the formula, *1 represents a bonding site that binds to the carbon atom bonded to R 11 in the formula (A1-1). *2 represents a bonding site that binds to L 2 in the formula (A1-1).)

[0103] Regarding the number of carbon atoms of the divalent organic group in L 2 in the formula (A1-1), there is no particular limitation, but it is preferably 1 to 10.

[0104] The divalent organic group in L 2 in the formula (A1-1) is, for example, a hydrocarbon group, and preferably a hydrocarbon group having 1 to 10 carbon atoms.

[0105] Regarding the divalent organic group in L 2 in the formula (A1-1), from the viewpoint of suitably obtaining the effects of the present invention, a divalent organic group having a benzene ring bonded to B (boron) in the formula (A1-1) is preferred, and a phenylene group is more preferred.

[0106] An example of the vinyl polymer (A1) containing the structural unit represented by the formula (A1-1) is obtained, for example, by homopolymerizing or copolymerizing a compound having a polymerizable unsaturated bond and an organoboric acid structure.

[0107] As the compound having a polymerizable unsaturated bond and an organoboric acid structure, for example, a compound represented by the following formula can be mentioned.

[0108]

[0109] An example of the vinyl polymer (A1) having the structural unit represented by the inclusion formula (A1-1) can be obtained, for example, by reacting a compound (C1) having an organic boric acid structure and a carboxyl group with a glycidyl (meth)acrylate polymer. The glycidyl (meth)acrylate polymer may be a homopolymer or a copolymer. Examples of the copolymer include a copolymer of glycidyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate and a copolymer of glycidyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0110]

[0111] (In the formula, R 11 , L 2 , R a and R b each have the same meaning as R 11 , L 2 , R a and R b in the formula (A1-1).)

[0112] The reaction can be carried out, for example, in the presence of a catalyst such as tetrabutylammonium bromide and the like.

[0113] Examples of the compound (C1) having an organic boric acid structure and a carboxyl group include the following compounds.

[0114]

[0115] The vinyl polymer (A1) may also have a structural unit other than the structural unit represented by the formula (A1-1). Examples of such a structural unit include the structural unit represented by the following formula (A1-2), the structural unit represented by the following formula (A1-3), and the like.

[0116]

[0117] (In the formula (A1-2), R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L 3 represents a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the above alkyl group and the above aryl group may be substituted with a hydroxyl group.

[0118] In the formula (A1-3), R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L 4represents a hydroxyl group or an amino group (-NH2). L 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. m1 represents an integer of 1 to 3. m2 represents an integer of 0 to 4. However, the sum of m1 and m2 is 1 to 5. When m1 is 2 or 3, multiple L 4 can be the same or different. When m2 is 2 to 4, multiple L 5 can be the same or different.)

[0119] R 12 The alkyl group having 1 to 10 carbon atoms represented by and L 3 The specific examples of the alkyl group having 1 to 10 carbon atoms represented by are as described above.

[0120] As the halogen atom in L 5 , for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be cited.

[0121] As the alkyl group having 1 to 6 carbon atoms in L 5 , for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, etc. can be cited.

[0122] As the alkoxy group having 1 to 6 carbon atoms in L 5 , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. can be cited.

[0123] As the aryl group having 6 to 40 carbon atoms, for example, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group, etc. can be cited.

[0124] As the monomers used for the derivative formula (A1-2), for example, the following compounds can be cited.

[0125]

[0126] As the monomers used for the derivative formula (A1-3), for example, the following compounds can be cited.

[0127]

[0128] Me represents a methyl group.

[0129] The proportion of the structural unit represented by the formula (A1-1) in the vinyl polymer (A1) is not particularly limited, but the molar ratio of the structural unit represented by the formula (A1-1) relative to all the structural units of the vinyl polymer (A1) can be, for example, 20 mol% to 100 mol%, and can be 20 mol% or more and less than 100 mol%.

[0130] The proportion of the structural unit represented by the formula (A1-2) in the vinyl polymer (A1) is not particularly limited, but the molar ratio of the structural unit represented by the formula (A1-2) relative to all the structural units of the vinyl polymer (A1) can be, for example, 0 mol% to 80 mol%, and can be more than 0 mol% and 80 mol% or less.

[0131] The vinyl polymer (A1) may also contain other structural units in addition to the structural unit represented by the formula (A1-1) and the structural unit represented by the formula (A1-2). In this case, the molar ratio of the other structural units in all the structural units of the vinyl polymer (A1) is, for example, more than 0 mol% and 20 mol% or less.

[0132] <<Polyester polymer (A2)>>

[0133] The case where the polymer (A) is a polyester polymer (A2) will be described.

[0134] The polyester polymer (A2) has, for example, the structure represented by the above formula (B1-2).

[0135] In addition, the polyester polymer (A2) has, for example, the structure represented by the following formula (A2-1).

[0136]

[0137] (In the formula (A2-1), R a and R b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a tolyl group. In addition, R a and R b may together form a ring structure having 3 to 6 carbon atoms.

[0138] R 1b represents a trivalent organic group.

[0139] * represents a bonding site.)

[0140] As R 1b , from the viewpoint of suitably obtaining the effects of the present invention, a trivalent group in which 3 hydrogen atoms are removed from a benzene ring is preferred.

[0141] The polyester-based polymer (A2) has, for example, a unit structure represented by the following formula (P).

[0142]

[0143] (In formula (P), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group.

[0144] Q 1 and Q 2 each independently represent a divalent organic group containing a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.

[0145] T 2 and T 3 each independently represent a single bond, an ester bond, or an ether bond.

[0146] L 2 and L 3 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted.

[0147] However, at least one of Q 1 and Q 2 has an organic boronic acid structure.)

[0148] Add a specific example of the unit structure represented by formula (P).

[0149] As Q 1 , the structure represented by the following formula (P-1) can be cited as an example.

[0150]

[0151] (In formula (P-1), X1 represents the following formula (P-1-1), the following formula (P-1-2), or the following formula (P-1-3).

[0152] Z1 and Z2 each independently represent a single bond or the following formula (P-1-4).

[0153] * represents a bonding site.)

[0154]

[0155] (In formulas (P-1-1) and (P-1-2), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group which may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may combine with each other to form a ring having 3 to 6 carbon atoms. * represents a bonding site. *1 represents a bonding site bonded to a carbon atom. *2 represents a bonding site bonded to a nitrogen atom.)

[0156] (In formula (P-1-3), R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group which may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. *1 represents a bonding site bonded to a carbon atom. *2 represents a bonding site bonded to a nitrogen atom.)

[0157]

[0158] (In formula (P-1-4), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. However, when m3 is 1, m1 and m2 are not both 0 at the same time. *3 represents a bonding site bonded to the nitrogen atom in formula (P-1).

[0159] *4 represents a bonding site.)

[0160] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0161] In the present specification, the alkyl group is not limited to a straight-chain form, and may be a branched-chain form or a cyclic form. Examples of the straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, and the like. Examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0162] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, a n-pentyloxy group, an isopropoxy group, and the like.

[0163] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0164] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, and the like.

[0165] In the present specification, examples of the alkynyl group include groups in which the double bond of the alkenyl group exemplified in the above “alkenyl group” is replaced with a triple bond.

[0166] In the present specification, examples of the alkenyloxy group include vinyloxy, 1-propenyloxy, 2-propenyloxy (allyloxy), 1-butenyloxy, isopentyloxy (prenyloxy group), and the like.

[0167] In the present specification, examples of the alkynyloxy group include 2-propynyloxy, 1-methyl-2-propynyloxy, 2-methyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, and the like.

[0168] In the present specification, examples of the acyl group include acetyl, propionyl, and the like.

[0169] In the present specification, examples of the aryloxy group include phenyloxy, naphthyloxy, and the like.

[0170] In the present specification, examples of the arylcarbonyl group include phenylcarbonyl, and the like.

[0171] In the present specification, examples of the aralkyl group include benzyl, phenethyl, and the like.

[0172] In the present specification, examples of the alkylene group include methylene, ethylene, 1,3-propylene, 2,2-propylene, 1-methylethylene, 1,4-butylene, 1-ethylideneethylene, 1-methylpropylene, 2-methylpropylene, 1,5-pentylene, 1-methylbutylene, 2-methylbutylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1-ethylpropylene, 2-ethylpropylene, 1,6-hexylene, 1,4-cyclohexylene, 1,8-octylene, 2-ethyloctylene, 1,9-nonylene, and 1,10-decylene, and the like.

[0173] Examples of the structure represented by the formula (P-1) include the following structures.

[0174]

[0175]

[0176] (* indicates a bonding site.)

[0177] As for Q 1and Q 2 The aromatic ring having 6 to 40 carbon atoms in 2 includes, for example, those derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, benzo[9,10]phenanthrene, phenalene, phenanthrene, indene, indane, indacene, pyrene, perylene, tetracene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene. Among them, those selected from benzene, naphthalene, and anthracene are preferred.

[0178] As -T in formula (P), 2 -L 2 -Q 2 -L 3 -T 3 -, for example, the structure shown in the above formula (A2-1) can be cited.

[0179] The molecular weight of polymer (A) is not particularly limited.

[0180] The lower limit of the weight-average molecular weight of polymer (A) is, for example, 500, 1,000, 2,000, or 3,000.

[0181] The upper limit of the weight-average molecular weight of polymer (A) is, for example, 30,000, 20,000, or 10,000.

[0182] The content of polymer (A) in the composition for forming an underlayer film of a resist is not particularly limited. From the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 99% by mass, more preferably 45% by mass to 95% by mass, and particularly preferably 50% by mass to 90% by mass, relative to the film constituent components.

[0183] It should be noted that in the present invention, the so-called film constituent components refer to the components contained in the composition other than the solvent.

[0184] <Solvent (B)>

[0185] There is no particular limitation on solvent (B), and it can be water or an organic solvent.

[0186] Examples of the organic solvent include alkylene glycol monoalkyl ethers, mono-carboxylic acid esters of alkylene glycol monoalkyl ethers, etc.

[0187] Examples of the alkylene of the alkylene glycol monoalkyl ether include alkylene having 2 to 4 carbon atoms.

[0188] Examples of the alkyl of the alkylene glycol monoalkyl ether include alkyl having 1 to 4 carbon atoms.

[0189] Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8.

[0190] Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like.

[0191] Examples of the alkylene of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether include alkylene having 2 to 4 carbon atoms.

[0192] Examples of the alkyl of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether include alkyl having 1 to 4 carbon atoms.

[0193] Examples of the mono-carboxylic acid of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether include saturated mono-carboxylic acids having 2 to 4 carbon atoms.

[0194] Examples of the saturated mono-carboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0195] Examples of the number of carbon atoms of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether include 5 to 10.

[0196] Examples of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

[0197] Examples of other organic solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

[0198] Among these solvents (B), alkylene glycol monoalkyl ethers and mono-carboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0199] These solvents (B) can be used alone or in combination of two or more.

[0200] The mass ratio of the organic solvent in the solvent (B) is not particularly limited, but is preferably 50% by mass to 100% by mass.

[0201] The content of the solvent (B) in the composition for forming the underlayer film of the resist is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.

[0202] <Crosslinking agent (C)>

[0203] There is no particular limitation on the crosslinking agent (C).

[0204] The crosslinking agent (C) has a structure different from that of the polymer (A).

[0205] As the crosslinking agent (C), aminoplast crosslinking agents and phenolic plastic crosslinking agents are preferred.

[0206] The aminoplast crosslinking agent is an addition condensate of a compound having an amino group such as melamine and guanamine with formaldehyde.

[0207] The so-called phenolic plastic crosslinking agent is an addition condensate of a compound having a phenolic hydroxyl group with formaldehyde.

[0208] As the crosslinking agent (C), for example, compounds having two or more of the following structures can be cited.

[0209]

[0210] (In the structure, R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bonding site.)

[0211] The bonding site binds to, for example, a nitrogen atom, a carbon atom constituting an aromatic hydrocarbon ring, etc.

[0212] As R 101 , a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure is preferred.

[0213]

[0214] (In the structure, R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bonding site.)

[0215] As the crosslinking agent (C), melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred. They can be used alone or in combination of two or more.

[0216] Examples of the melamine compound include hexahydroxymethylmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexahydroxymethylmelamine are methoxymethylated or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 4 hydroxymethyl groups of hexahydroxymethylmelamine are acyloxymethylated or a mixture thereof, and the like.

[0217] Examples of the guanamine compound include tetrahydroxymethylguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylguanamine are methoxymethylated or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylguanamine are acyloxymethylated or a mixture thereof, and the like.

[0218] Examples of the glycoluril compound include tetrahydroxyethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetrahydroxyethyl glycoluril are methoxymethylated or a mixture thereof, a compound in which 1 to 4 hydroxymethyl groups of tetrahydroxyethyl glycoluril are acyloxymethylated or a mixture thereof, and the like.

[0219] In addition, as the glycoluril compound, a glycoluril derivative represented by the following formula (1E) can also be used as an example.

[0220]

[0221] (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.)

[0222] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formula (1E-1) to formula (1E-6).

[0223]

[0224] The glycoluril derivative represented by formula (1E) is obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0225]

[0226] (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.)

[0227]

[0228] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0229] As the glycoluril derivative represented by the above formula (2E), compounds represented by the following formula (2E-1) to formula (2E-4) can be cited as examples.

[0230] Furthermore, as the compound represented by the above formula (3d), compounds represented by the following formula (3d-1) and formula (3d-2) can be cited as examples.

[0231]

[0232] As the urea compound, for example, tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolurea are methoxymethylated or a mixture thereof, tetramethoxyethylurea, etc. can be cited.

[0233] As the compound having a phenolic hydroxyl group, for example, a compound represented by the following formula (G-1) or formula (G-2) can be cited.

[0234]

[0235] (In formula (G-1) and formula (G-2), Q 1 represents a single bond or an m1-valent organic group.

[0236] R 1 and R 4 each represent an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms with an alkoxy group having 1 to 10 carbon atoms.

[0237] R 2 and R 5 each represent a hydrogen atom or a methyl group.

[0238] R 3 and R 6 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0239] n1 represents an integer of 1 ≤ n1 ≤ 3, n2 represents an integer of 2 ≤ n2 ≤ 5, n3 represents an integer of 0 ≤ n3 ≤ 3, n4 represents an integer of 0 ≤ n4 ≤ 3, and n1, n2, n3, n4 represent an integer of 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0240] n5 represents an integer of 1 ≤ n5 ≤ 3, n6 represents an integer of 1 ≤ n6 ≤ 4, n7 represents an integer of 0 ≤ n7 ≤ 3, n8 represents an integer of 0 ≤ n8 ≤ 3, and n5, n6, n7, n8 represent an integer of 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0241] m1 represents an integer of 2 to 10.)

[0242] In addition, examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (G-3) or formula (G-4).

[0243] The compound represented by formula (G-1) or formula (G-2) may be a substance obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0244]

[0245] (In formula (G-3) and formula (G-4), Q 2 represents a single bond or an m2-valent organic group.

[0246] R 8 、R 9 、R 11 and R 12 each represent a hydrogen atom or a methyl group.

[0247] R 7 and R 10 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0248] n9 represents an integer of 1 ≤ n9 ≤ 3, n 10 represents an integer of 2 ≤ n 10 ≤ 5, n 11 represents an integer of 0 ≤ n 11 ≤ 3, n 12 represents an integer of 0 ≤ n 12 ≤ 3, and n9, n 10 、n 11 、n 12 represent an integer of 3 ≤ (n9 + n 10 + n 11 + n 12 ) ≤ 6.

[0249] n 13 represents an integer of 1 ≤ n 13 ≤ 3, n 14 represents an integer of 1 ≤ n 14 ≤ 4, n 15 represents an integer of 0 ≤ n 15 ≤ 3, n 16 represents an integer of 0 ≤ n 16 ≤ 3, and n 13 、n 14 、n 15 、n 16 represent an integer of 2 ≤ (n 13 + n 14 + n 15 + n 16 ) ≤ 5.

[0250] m2 represents an integer from 2 to 10.)

[0251] As Q 2 The m2-valent organic group in it may be, for example, an m2-valent organic group having 1 to 4 carbon atoms.)

[0252] As the compound represented by formula (G-1) or formula (G-2), for example, the following compounds can be cited.)

[0253]

[0254]

[0255] As the compound represented by formula (G-3) or formula (G-4), for example, the following compounds can be cited.)

[0256]

[0257]

[0258] The above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd. As products, for example, the trade name TMOM-BP of Asahi Organic Materials Industry Co., Ltd. can be cited.)

[0259] Among them, glycoluril compounds are preferred. Specifically, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof are preferred, and tetramethoxymethyl glycoluril is more preferred.)

[0260] The molecular weight of the crosslinking agent (C) is not particularly limited, but it is preferably 500 or less.)

[0261] The content of the crosslinking agent (C) in the composition for forming an anti-resist lower layer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, preferably 5% by mass to 60% by mass, relative to the polymer (A).)

[0262] <Curing catalyst (D)>

[0263] Regarding the curing catalyst (D) contained as an optional component in the composition for forming an anti-resist lower layer film, both thermal acid generators and photoacid generators can be used, but thermal acid generators are preferably used.)

[0264] As thermal acid generators, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine -p-toluenesulfonate (pyridine -p-toluenesulfonic acid), pyridine Phenol sulfonic 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, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, N-methylmorpholine-5-sulfosalicylic acid and other sulfonic acid compounds and carboxylic acid compounds.

[0265] As the photoacid generator, for example, salt compounds, sulfimide compounds, disulfonyldiazomethane compounds and the like can be mentioned.

[0266] As the salt compound, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate and other iodonium salt compounds, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate and other sulfonium salt compounds, etc.

[0267] As the sulfimide compound, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenedicarboximide and the like can be mentioned.

[0268] As the disulfonyldiazomethane compound, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane and the like can be mentioned.

[0269] The curing catalyst (D) can be used alone, or two or more kinds can be used in combination.

[0270] When the curing catalyst (D) is used, the content ratio of the curing catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass.

[0271] <Other components>

[0272] In the composition for forming an underlayer film of a resist, 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.

[0273] 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 aryl 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; 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 DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited, trade name), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., trade name); and silicone oxide polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0274] 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.

[0275] These surfactants may be added alone, or may be added in combination of two or more.

[0276] The solid components contained in the composition for forming an underlayer film of a resist of the present invention, that is, the components other than the above solvents, are, for example, 0.01% by mass to 10% by mass.

[0277] (Underlayer film of resist)

[0278] The underlayer film of a resist of the present invention is a cured product of the above composition for forming an underlayer film of a resist.

[0279] The underlayer film of a resist can be manufactured, for example, by coating the above composition for forming an underlayer film of a resist on a semiconductor substrate and then baking.

[0280] Examples of the semiconductor substrate for forming the underlayer film of the coating resist include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0281] In the case of using a semiconductor substrate having an inorganic film formed on the 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, for example, 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.

[0282] On such a semiconductor substrate, the composition for forming the underlayer film of the 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 the underlayer film of the 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.

[0283] Examples of the film thickness of the underlayer film of the resist include 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (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), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0284] The method for measuring the film thickness of the underlayer film of the resist in this specification is as described below.

[0285] · Name of measuring device: Ellipsometric film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0286] · SWE (Single Wavelength Ellipsometer) mode

[0287] · Arithmetic mean of 8 points (for example, measuring 8 points at 1 cm intervals along the X direction of the wafer)

[0288] (Laminate)

[0289] The laminate of the present invention includes a semiconductor substrate and the underlayer film for resist of the present invention.

[0290] Examples of the semiconductor substrate include the above-mentioned semiconductor substrate.

[0291] The underlayer film for resist is disposed, for example, on the semiconductor substrate.

[0292] (Method for manufacturing semiconductor device, method for forming pattern)

[0293] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0294] · A step of forming an underlayer film for resist on a semiconductor substrate using the composition for forming an underlayer film for resist of the present invention; and

[0295] · A step of forming a resist film on the underlayer film for resist

[0296] The method for forming a pattern of the present invention includes at least the following steps.

[0297] · A step of forming an underlayer film for resist on a semiconductor substrate using the composition for forming an underlayer film for resist of the present invention;

[0298] · A step of forming a resist film on the underlayer film for resist;

[0299] · A step of irradiating light or electron beam to the resist film, and then developing the resist film to obtain a resist pattern; and

[0300] · A step of using the resist pattern as a mask to etch the underlayer film for resist.

[0301] Generally, a resist layer is formed on the underlayer film for resist.

[0302] As the film thickness of the resist layer, it is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less. In addition, as the film thickness of the resist layer, it is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.

[0303] As a resist formed on an underlayer film of a resist by a known method (e.g., coating and baking of a resist composition), there is no particular limitation as long as it responds to light or electron beam (EB) used for irradiation. Both negative-type photoresists and positive-type photoresists can be used.

[0304] It should be noted that, in this specification, a resist responsive to EB is also referred to as a photoresist.

[0305] Examples of photoresists include positive-type photoresists composed of novolak resin and 1,2-naphthoquinone diazide sulfonate, chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases upon decomposition by an acid and a photoacid generator, chemically amplified photoresists composed of a low molecular compound whose alkali dissolution rate of the photoresist increases upon decomposition by an acid, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases upon decomposition by an acid, a low molecular compound whose alkali dissolution rate of the photoresist increases upon decomposition by an acid, and a photoacid generator, and resists containing a metal element. Examples thereof include 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. In addition, examples include fluorine atom-containing polymer-based 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).

[0306] In addition, so-called resist compositions 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., such as resist compositions, radiation-sensitive resin compositions, compositions for forming high-resolution patterns based on organometallic solutions, and metal-containing resist compositions, are used, but are not limited to these.

[0307] Examples of the resist composition include the following compositions.

[0308] A radiation-sensitive or actinic ray-sensitive resin composition comprising resin A and a compound represented by the following general formula (121), wherein resin A has a repeating unit having an acid-decomposable group in which a polar group is protected by a protecting group removable by the action of an acid.

[0309]

[0310] In general formula (121), m represents an integer of 1 to 6.

[0311] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0312] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0313] L2 represents an alkylene group which may have a substituent or a single bond.

[0314] W1 represents a cyclic organic group which may have a substituent.

[0315] M + represents a cation.

[0316] 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.

[0317] 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 (31) and a second structural unit containing an acid dissociable group represented by the following formula (32).

[0318]

[0319] (In formula (31), 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 thiol 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. In formula (32), 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 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)

[0320] 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 the following formula, and a structural unit having an acid-labile group.

[0321]

[0322] [In the formula,

[0323] 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 site to -Ar, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from a hydroxyl group and a carboxyl group.]

[0324] Examples of the resist film include the following resist films.

[0325] A resist film containing a base resin, wherein the base resin contains 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.

[0326]

[0327] (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.)

[0328] Examples of the resist material include the following resist materials.

[0329] A resist material containing a polymer having a repeating unit represented by the following formula (b1) or formula (b2).

[0330]

[0331] (In formula (b1) and formula (b2), R A is a hydrogen atom or a methyl group. X1 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, provided that at least one 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 sulfone 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 combine to form a ring together with the sulfur atom to which they are attached.)

[0332] A resist material comprising a base resin, said base resin comprising: a polymer containing a repeating unit represented by the following formula (a).

[0333]

[0334] (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. u is an integer of 0 to 3. However, m + u is an integer of 1 to 4.)

[0335] A resist composition that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid.

[0336] It contains a base material component (A) whose solubility in a developer changes by the action of an acid and a fluorine additive component (F) that exhibits decomposability in an alkaline developer.

[0337] The above-mentioned fluorine additive component (F) contains a fluororesin component (F1), and the above-mentioned fluororesin component (F1) has a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0338]

[0339] [In the 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 of 0 to 2. * is a bonding site.]

[0340] The above-mentioned 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).

[0341]

[0342] [In the formulas (f1-1) and (f1-2), R are each 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 site. A aryl is a divalent aromatic cyclic group that 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.]

[0343] Examples of the coating, coating solution, and coating composition include the following coating, coating solution, and coating composition.

[0344] A coating that contains a metal oxo-hydroxy network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0345] An inorganic oxygen / hydroxy-based composition.

[0346] A coating solution that contains: 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 a hydrocarbon group 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).

[0347] 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 coating solution containing 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).

[0348] An aqueous solution of an inorganic pattern forming precursor comprising a mixture of water and a radiation-sensitive ligand, the radiation-sensitive ligand comprising a metal lower oxide cation, a polyatomic inorganic anion, and a peroxide group).

[0349] Irradiation with light or electron beams is carried out, for example, through a mask (reticle) for forming a prescribed pattern. For example, i-rays, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. The composition for forming an underlayer film of a resist of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably applied for EUV (extreme ultraviolet) exposure).

[0350] There is no particular limitation on the irradiation energy of the electron beam and the exposure amount of light).

[0351] Baking (PEB: Post Exposure Bake) can also be carried out after irradiation with light or electron beams and before development).

[0352] There is no particular limitation on the baking temperature, but it is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C).

[0353] There is no particular limitation on the baking time, but it is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes).

[0354] For development, an alkaline developer can be used, for example).

[0355] Examples of the development temperature include 5°C to 50°C).

[0356] As the development time, for example, 10 seconds to 300 seconds can be cited.

[0357] As the alkaline developer, for example, aqueous solutions of 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, an appropriate amount of alcohols such as isopropanol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the above-mentioned bases and used. Among them, the preferred developer is an aqueous solution of a quaternary ammonium salt, and more preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Further, a surfactant or the like can be added to these developers. A method of developing with an organic solvent such as butyl acetate instead of the alkaline developer and developing the portion where the base dissolution rate of the photoresist is not increased can also be used.

[0358] Next, using the formed resist pattern as a mask, the underlying resist film is etched. The etching can be dry etching or wet etching, but dry etching is preferred.

[0359] When the above-mentioned inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. When the above-mentioned inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate can be processed through a process of processing the semiconductor substrate by a known method (dry etching method, etc.) to manufacture a semiconductor element.

[0360] Examples

[0361] Next, examples are given to specifically illustrate the content of the present invention, but the present invention is not limited to these.

[0362] <Measurement of Molecular Weight>

[0363] The weight average molecular weights of the polymers shown in Synthesis Examples 1 to 5, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 in the following description of this specification are the measurement results obtained by gel permeation chromatography (hereinafter, simply referred to as GPC). A GPC device manufactured by Tosoh Corporation was used in the measurement, and the measurement conditions and the like are as described below.

[0364] · GPC column: TSKgel Super-Multipore HZ-N (2 columns)

[0365] · Column temperature: 40 °C

[0366] · Solvent: Tetrahydrofuran (THF)

[0367] · Flow rate: 0.35 ml / min

[0368] · Standard specimen: Polystyrene (manufactured by Tosoh Corporation)

[0369] <Synthesis Example 1>

[0370] 18.30 g of glycidyl methacrylate-2-hydroxyethyl methacrylate copolymer (manufactured by Osaka Organic Chemical Industry Co., Ltd., propylene glycol monomethyl ether solution), 1.43 g of 4-carboxyphenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutylammonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) 0.11 g were added to 6.71 g of propylene glycol monomethyl ether (hereinafter, abbreviated as PGME in this specification) in a reaction vessel and dissolved. After replacing the reaction vessel with nitrogen, the reaction was carried out at 80 °C for 24 hours to obtain a solution containing Polymer 1. GPC analysis was performed, and as a result, the obtained Polymer 1 had a weight-average molecular weight of 7,600 and a dispersity of 4.2 in terms of standard polystyrene. The structure present in Polymer 1 is shown in the following formula.

[0371]

[0372] <Synthesis Example 2>

[0373] 5.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 3.93 g of 3,5-dicarboxyphenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutylammonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) 0.45 g were added to 14.07 g of PGME in a reaction vessel and dissolved. After replacing the reaction vessel with nitrogen, the reaction was carried out at 140 °C for 24 hours to obtain a solution containing Polymer 2. GPC analysis was performed, and as a result, the obtained Polymer 2 had a weight-average molecular weight of 870 and a dispersity of 1.3 in terms of standard polystyrene. The structure present in Polymer 2 is shown in the following formula.

[0374]

[0375] <Synthesis Example 3>

[0376] 3.00 g of 4-vinylphenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.38 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 13.50 g of PGME to obtain a solution. The resulting solution was added to a reaction vessel maintained at 80 °C containing 5.63 g of PGME, and the mixture was reacted for 24 hours to obtain a solution containing Polymer 3. GPC analysis was performed, and as a result, the resulting Polymer 3 had a weight-average molecular weight of 13,300 and a dispersity of 3.1 in terms of standard polystyrene. The structure present in Polymer 3 is shown in the following formula.

[0377]

[0378] <Synthesis Example 4>

[0379] 2.00 g of 4-vinylphenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.95 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.52 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 19.62 g of PGME to obtain a solution. The resulting solution was added to a reaction vessel maintained at 60 °C containing 11.54 g of PGME, and the mixture was reacted for 24 hours to obtain a solution containing Polymer 4. GPC analysis was performed, and as a result, the resulting Polymer 4 had a weight-average molecular weight of 16,500 and a dispersity of 5.0 in terms of standard polystyrene. The structure present in Polymer 4 is shown in the following formula.

[0380]

[0381] <Synthesis Example 5>

[0382] 2.00 g of 4-vinylphenylboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.76 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.66 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 25.02 g of PGME to obtain a solution. The resulting solution was added to a reaction vessel maintained at 60 °C containing 14.72 g of PGME, and the mixture was reacted for 24 hours to obtain a solution containing Polymer 5. GPC analysis was performed, and as a result, the resulting Polymer 5 had a weight-average molecular weight of 25,100 and a dispersity of 6.1 in terms of standard polystyrene. The structure present in Polymer 5 is shown in the following formula.

[0383]

[0384] <Comparative Synthesis Example 1>

[0385] 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of PGME in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 130 °C for 24 hours to obtain a solution containing Comparative Polymer 1. GPC analysis was performed, and as a result, the obtained Comparative Polymer 1 had a weight-average molecular weight of 6,800 in terms of standard polystyrene and a dispersity of 4.8. The structure present in Comparative Polymer 1 is shown in the following formula.

[0386]

[0387] <Comparative Synthesis Example 2>

[0388] 6.00 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.50 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.43 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 20.82 g of propylene glycol monomethyl ether acetate (hereinafter, simply referred to as PGMEA in this specification) to obtain a solution. The obtained solution was added to a reaction vessel maintained at 140 °C containing 14.87 g of PGMEA and reacted for 24 hours to obtain a solution containing Comparative Polymer 2. GPC analysis was performed, and as a result, the obtained Comparative Polymer 2 had a weight-average molecular weight of 7,700 in terms of standard polystyrene and a dispersity of 2.6.

[0389] The structure present in Comparative Polymer 2 is shown in the following formula.

[0390]

[0391] (Preparation of Composition for Forming Antireflective Underlayer Film)

[0392] (Examples, Comparative Examples)

[0393] The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 5, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 above were mixed in the proportions shown in Tables 1-1 and 1-2 so that the solid content was about 0.18 mass% to 0.20 mass%, and filtered through a 0.1 μm fluororesin filter to prepare compositions for forming antireflective underlayer films, respectively.

[0394] The meanings of the abbreviations in Tables 1-1 and 1-2 are as follows.

[0395] ·PL-LI: Tetramethoxymethyl glycoluril

[0396] ·PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl] (Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]) - (the following structural formula)

[0397]

[0398] ·PGME-BIP-A: Phenol, 4,4’-(1-methylethylidene)bis[2,6-bis[(2-methoxy-1-methyl ethoxy)methyl] (Phenol, 4,4’-(1-methylethylidene)bis[2,6-bis[(2-methoxy-1-methyl ethoxy)methyl]) - (the following structural formula)

[0399]

[0400] TMOM-BP: 3,3’,5,5’-tetrakis(methoxymethyl)-[1,1’-biphenyl]-4,4’-diol (the following structural formula)

[0401]

[0402] ·PyPSA: Pyridine -p-Hydroxybenzenesulfonic acid

[0403] ·R-30N: Surfactant (manufactured by DIC Corporation)

[0404] ·PGMEA: Propylene glycol monomethyl ether acetate

[0405] ·PGME: Propylene glycol monomethyl ether

[0406] The addition amount of each component is expressed in parts by mass, and the solvent is expressed in composition ratio.

[0407] [Table 1-1]

[0408]

[0409] [Table 1-2]

[0410]

[0411] (Dissolution test in photoresist solvent)

[0412] The resist underlayer film-forming compositions of Examples 1 to 6, Comparative Example 1, and Comparative Example 2 were each applied onto a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205 °C or 240 °C for 60 seconds to obtain a film with a film thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (mass ratio), which is the solvent used for the photoresist. When the film thickness changed to the following, it was designated as "good", and when it exceeded it was designated as "bad". The baking temperature and the results are shown in Table 2.

[0413] [Table 2]

[0414] Baking temperature Dissolution test Example 1 205℃ Good Example 2 205℃ Good Example 3 240℃ Good Example 4 205℃ Good Example 5 205℃ Good Example 6 205℃ Good Comparative Example 1 205℃ Good Comparative Example 2 205℃ Good

[0415] (Evaluation of resist pattern formation)

[0416] [Formation test of resist pattern using an electron beam lithography apparatus]

[0417] The resist underlayer film-forming compositions of Examples 1 to 6, Comparative Example 1, and Comparative Example 2 were each applied onto a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205 °C or 240 °C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. An EUV positive resist solution was spin-coated onto this resist underlayer film and heated at 130 °C for 60 seconds to form an EUV resist film. Using an electron beam lithography apparatus (ELS-G130), the resist film was exposed under specified conditions. After exposure, baking was performed at 100 °C for 60 seconds (PEB), and it was cooled on a cooling plate until room temperature. Paddle development was performed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a hole size of 16 nm to 26 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used for measuring the length of the resist pattern.

[0418] Regarding the photoresist pattern obtained by such operations, it was checked whether a 23-nm contact hole (C / H) could be formed. In all cases of Examples 1 to 6, formation of a 23-nm C / H pattern was confirmed. In addition, the charge amount at which a 23-nm contact hole was formed was set as the optimum irradiation energy (μC / cm 2 ). The relative value of the optimum irradiation energy with respect to when the optimum irradiation energy of Comparative Example 1 was set to 1.00 is shown in Table 3. A decrease in the optimum irradiation energy was confirmed for Examples 1 to 6 compared with Comparative Example 1 and Comparative Example 2.

[0419] [Table 3]

[0420]

Claims

1. A composition for forming an underlayer film of a resist, which comprises: a polymer (A) having an organic boronic acid structure, and a solvent (B).

2. The composition for forming an underlayer film of a resist according to claim 1, wherein the organic boronic acid structure is an arylboronic acid structure.

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

4. The composition for forming an underlayer film of a resist according to claim 1, which further comprises a crosslinking agent (C).

5. The composition for forming an underlayer film of a resist according to claim 4, wherein the crosslinking agent (C) is at least one selected from aminoplast crosslinking agents and phenolic plastic crosslinking agents.

6. The composition for forming an underlayer film of a resist according to claim 1, which further comprises a curing catalyst (D).

7. An underlayer film of a resist, which is a cured product of the composition for forming an underlayer film of a resist according to any one of claims 1 to 6.

8. A laminate, which comprises a semiconductor substrate, and the underlayer film of a resist according to claim 7.

9. A method for manufacturing a semiconductor device, which comprises the following steps: a step of forming an underlayer film of a resist on a semiconductor substrate using the composition for forming an underlayer film of a resist according to any one of claims 1 to 6; and a step of forming a resist film on the underlayer film of a resist.

10. A method for forming a pattern, which comprises the following steps: a step of forming an underlayer film of a resist on a semiconductor substrate using the composition for forming an underlayer film of a resist according to any one of claims 1 to 6; a step of forming a resist film on the underlayer film of a resist; a step of irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and a step of using the resist pattern as a mask to etch the underlayer film of a resist.

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