Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film contains a polymer (A), a compound (B) having a hydrophobic substituent, and a solvent (C).

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 manufacture of conventional semiconductor devices, photolithography is used for microfabrication. The microfabrication is a process of forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating actinic rays such as ultraviolet rays through a mask pattern depicting a pattern of components thereon, developing, and using the obtained photoresist pattern as a protective film to perform substrate etching on the substrate, thereby forming fine irregularities corresponding to the photoresist pattern on the substrate surface. In recent years, with the development 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) used in the past, the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) has also been studied in the most advanced microfabrication. Along with this, poor formation of the resist pattern due to the influence of the semiconductor substrate or the like has become a major problem. Therefore, in order to solve this problem, methods of providing an underlayer film for a resist between the resist and the semiconductor substrate have been widely studied.

[0003] Patent Document 1 discloses an underlayer film-forming composition 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, not being miscible with the resist film formed on the upper layer (insoluble in the resist solvent) and being able to form a fine resist pattern with high sensitivity can be cited.

[0011] The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a composition for forming an underlayer film for a resist, the underlayer film for a resist capable of forming a fine resist pattern with high sensitivity, and a method for manufacturing an underlayer film for a resist, a laminate, a semiconductor device, and a pattern forming method using the composition for forming an underlayer film for a resist.

[0012] [Means for Solving the Problems]

[0013] As a result of intensive studies by the present inventors to solve the above problems, matters capable of solving the above problems were found, and the present invention having the following content was completed.

[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), a compound (B) having a hydrophobic substituent, and a solvent (C).

[0016] [2]. The composition for forming an underlayer film for a resist according to [1], wherein the polymer (A) is at least any one of an isocyanuric acid-based polymer, a polyester-based polymer, an acrylic acid-based polymer, and a polyether.

[0017] [3]. The composition for forming an underlayer film for a resist according to [1] or [2], wherein the polymer (A) is a polymer having a hydroxyl group in the unit structure.

[0018] [4]. The composition for forming an underlayer film for a resist according to any one of [1] to [3], wherein the hydrophobic substituent of the compound (B) is a substitutable aryl group or a substitutable alkyl group having 1 to 10 carbon atoms.

[0019] [5]. The composition for forming an underlayer film for a resist according to any one of [1] to [4], wherein the solvent (C) contains at least one selected from alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

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

[0021] [7]. The composition for forming an underlayer film for a resist according to [6], wherein the crosslinking agent (D) is at least one selected from aminoplast crosslinking agents and phenoplast crosslinking agents.

[0022] [8]. The composition for forming an underlayer film for a resist according to any one of [1] to [7], further comprising a curing catalyst (E).

[0023] [9]. A resist underlayer film is a cured product of a composition for forming a resist underlayer film described in any one of [1] to [8].

[0024]

[10] . A laminate includes a semiconductor substrate and the resist underlayer film described in [9].

[0025]

[11] . A method for manufacturing a semiconductor device includes:

[0026] a step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film described in any one of [1] to [8], and

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

[0028]

[12] . A patterning method includes:

[0029] a step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film described in any one of [1] to [8],

[0030] a step of forming a resist film on the resist underlayer film,

[0031] a step of irradiating the resist film with light or an electron beam, 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] [Advantages of the Invention]

[0034] According to the present invention, there can be provided a composition for forming a resist underlayer film capable of forming a resist underlayer film capable of forming a fine resist pattern with high sensitivity, and a resist underlayer film, a laminate, a method for manufacturing a semiconductor device, and a patterning method using the composition for forming a resist underlayer film. Detailed Description

[0035] (Composition for Forming Resist Underlayer Film)

[0036] The composition for forming a resist underlayer film of the present invention includes a polymer (A), a compound (B), and a solvent (C).

[0037] The composition for forming a resist underlayer film may also include a crosslinking agent (D), a curing catalyst (E), and the like.

[0038] By including the compound (B) having a hydrophobic substituent in the composition for forming a resist underlayer film, a fine resist pattern can be formed with high sensitivity as compared with the case where the compound (B) having a hydrophobic substituent is not included.

[0039] <Polymer (A)>

[0040] There is no particular limitation on the polymer (A).

[0041] The polymer (A) is, for example, an organic polymer.

[0042] The polymer (A) is, for example, an isocyanuric acid-based polymer. The isocyanuric acid-based polymer refers to a polymer having the following isocyanuric acid skeleton.

[0043]

Chemical Formula 1

[0044]

[0045] (In the formula, * represents a linking bond.)

[0046] Furthermore, one of the linking bonds represented by * may also be bonded to a hydrogen atom.

[0047] Furthermore, the polymer (A) is, for example, a polyester-based polymer. The 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.

[0048] In addition, when a polymer has an isocyanuric acid skeleton and an ester bond in the main chain, this polymer is an isocyanuric acid-based polymer and also a polyester-based polymer.

[0049] Furthermore, the polymer (A) is, for example, an acrylic acid-based polymer. The acrylic acid-based polymer is, for example, a polymer formed by polymerizing the polymerizable unsaturated bonds of a compound containing a group having a polymerizable unsaturated bond. The acrylic acid-based polymer may be a homopolymer or a copolymer. Examples of the group having a polymerizable unsaturated bond include, for example, (meth)acryloyl, vinylaryl (for example, styryl), vinyloxy, allyl, and the like.

[0050] Furthermore, the polymer (A) is, for example, a polyether. The polyether is, for example, a reaction product of a compound having two phenolic hydroxyl groups and a compound having two epoxy groups.

[0051] Examples of the polyether include, for example, the polymers described in WO2022 / 071468. Such a polymer is, for example, a polymer derived from a compound (B) represented by the following formula (11).

[0052]

Chemical Formula 2

[0053]

[0054] (In formula (11), Y 1represents a single bond, an oxygen atom, a sulfur atom, an alkylene group or a sulfonyl 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, T 1 and T 2 represents an alkyl group having 1 to 10 carbon atoms, and n1 and n2 each independently represent an integer of 0 to 4.)

[0055] The polymer is, for example, a reaction product of compound (B) and compound (C) capable of reacting with compound (B).

[0056] 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.

[0057] Polymer (A) may also be, for example, a polymer having a unit structure represented by the following formula (P). The polymer having a unit structure represented by the following formula (P) may also be, for example, the polymer described in WO2022 / 196662 (the polymer having a unit structure represented by formula (P)).

[0058]

Chemical formula 3

[0059]

[0060] (In formula (P), A1, A2, A3, A4, A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group.

[0061] 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.

[0062] T 2 and T 3 each independently represent a single bond, an ester bond or an ether bond.

[0063] 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.)

[0064] Specific examples of the unit structure represented by formula (P) are additionally described.

[0065] As Q 1 , the structure represented by the following formula (P-1) can be listed as an example.

[0066]

Chemical formula 4

[0067]

[0068] (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).

[0069] Z1 and Z2 each independently represent a single bond or the following formula (P-1-4).

[0070] (* represents a linking bond.)

[0071] [Chemical Formula 5]

[0072]

[0073] (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, and the phenyl group may be substituted by 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 also be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a linking bond. *1 represents a linking bond bonded to a carbon atom. *2 represents a linking bond bonded to a nitrogen atom.

[0074] 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, and the phenyl group may be substituted by 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 linking bond bonded to a carbon atom. *2 represents a linking bond bonded to a nitrogen atom.)

[0075] [Chemical Formula 6]

[0076]

[0077] (In formula (P-1-4), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2. However, when m3 is 1, m1 and m2 are not both 0 at the same time. *3 represents a linking bond bonded to the nitrogen atom in formula (P-1). *4 represents a linking bond.)

[0078] In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0079] In this specification, as the alkyl group, it is not limited to linear, and can be branched or cyclic. As the linear or branched alkyl group, for example, methyl, ethyl, isopropyl, tert-butyl, n-hexyl, etc. can be cited. As the cyclic alkyl group (cycloalkyl), for example, cyclobutyl, cyclopentyl, cyclohexyl, etc. can be cited.

[0080] In this specification, as the alkoxy group, for example, methoxy, ethoxy, n-pentyloxy, isopropoxy, etc. can be cited.

[0081] In this specification, as the alkylthio group, for example, methylthio, ethylthio, n-pentylthio, isopropylthio, etc. can be cited.

[0082] In this specification, as the alkenyl group, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc. can be cited.

[0083] In this specification, as the alkynyl group, a group in which the double bond of the alkenyl group exemplified in the above "alkenyl group" is changed to a triple bond can be cited.

[0084] In this specification, as the alkenyloxy group, for example, vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, pentyloxy, etc. can be cited.

[0085] In this specification, as the alkynyloxy group, for example, 2-propynyloxy, 1-methyl-2-propynyloxy, 2-methyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, etc. can be cited.

[0086] In this specification, as the acyl group, for example, acetyl, propionyl, etc. can be cited.

[0087] In this specification, as the aryloxy group, for example, phenoxy, naphthyloxy, etc. can be cited.

[0088] In this specification, as the arylcarbonyl group, for example, phenylcarbonyl, etc. can be cited.

[0089] In this specification, as the aralkyl group, for example, benzyl, phenethyl, etc. can be cited.

[0090] In this specification, examples of the alkylene group include methylene, ethylene, 1,3-propylene, 2,2-propylene, 1-methylethylene, 1,4-butylene, 1-ethyl ethylene, 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-ethyl octylene, 1,9-nonylene, 1,10-decylene, and the like.

[0091] Examples of the structure represented by the formula (P-1) include the following structures.

[0092]

Chemical Formula 7

[0093]

[0094]

Chemical Formula 8

[0095]

[0096]

Chemical Formula 9

[0097]

[0098]

Chemical Formula 10

[0099]

[0100]

Chemical Formula 11

[0101]

[0102]

Chemical Formula 12

[0103]

[0104] (* indicates a connecting bond.)

[0105] As for Q 1 and Q 2 Examples of the aromatic ring having 6 to 40 carbon atoms in Q include aromatic rings derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene. Among these, those preferably selected from benzene, naphthalene, and anthracene.

[0106] As for Q1 and Q 2 The divalent organic group having an aromatic ring structure with 6 to 40 carbon atoms in Q may include, for example, a divalent aromatic group with 6 to 40 carbon atoms which may also have substituents.

[0107] Examples of the substituent may include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, etc.

[0108] As -T in formula (P) 2 -L 2 -Q 2 -L 3 -T 3 -, the following divalent organic groups may be included, for example.

[0109]

Chemical formula 13

[0110]

[0111]

Chemical formula 14

[0112]

[0113]

Chemical formula 15

[0114]

[0115] (* indicates a connecting bond.)

[0116] The polymer (A) may also be, for example, a polymer described in WO2009 / 008446, WO2011 / 074494, WO2013 / 018802, etc. described below.

[0117] · A polymer having a repeating unit structure represented by the following formula (1) described in WO2009 / 008446.

[0118]

Chemical formula 16

[0119]

[0120] (In formula (1), R1 represents a methoxy group, an alkyl group with 1 to 13 carbon atoms, or a halogen atom, n represents an integer from 0 to 4, R2 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group with 1 to 13 carbon atoms, or a halogen atom, X represents an ether bond or an ester bond, A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group between two carbon atoms.)

[0121] · A polymer having a repeating unit structure represented by the following formula (1) described in WO2011 / 074494.

[0122] [Chemical Formula 17]

[0123]

[0124] (In formula (1), X represents an ester bond or an ether bond. A1, A2, A3, A4, A5, and A6 分 each represent a hydrogen atom, a methyl group, or an ethyl group, and Q represents the following formula (2) or the following formula (3).)

[0125] [Chemical Formula 18]

[0126]

[0127] (In formulas (2) and (3), Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthracenylene group, and the phenylene group, naphthylene group, and anthracenylene group may each be substituted with a group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. n1 and n2 each represent a number of 0 or 1, and X1 represents the following formula (4), the following formula (5), or the following formula (6).)

[0128] [Chemical Formula 19]

[0129]

[0130] (In formulas (4), (5), and (6), R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the benzyl group and phenyl group may each be substituted with a group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. Furthermore, R 1 and R 2 may also be bonded to each other to form a ring having 3 to 6 carbon atoms, and R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and the benzyl group and phenyl group may each be substituted with a group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms.)

[0131] ·A polymer having the structure of the following formula (1a) described in WO2013 / 018802.

[0132] [Chemical Formula 20]

[0133]

[0134] (In formula (1a), A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, X1 represents the following formula (2), the following formula (3), the following formula (4), or the following formula (0). Q represents the following formula (5) or the following formula (6).)

[0135] [Chemical formula 21]

[0136]

[0137] (In formulas (2), (3), (4), and (0), R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the benzyl group, and the phenyl group may also be substituted with a 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, a hydroxyl group, a carboxyl group, and an alkylthio group having 1 to 6 carbon atoms. Furthermore, R1 and R2 may also be bonded to each other to form a ring having 3 to 6 carbon atoms. R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may also be substituted with a 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, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms.)

[0138] [Chemical formula 22]

[0139]

[0140] (In formulas (5) and (6), Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may also be substituted with a group formed by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a combination thereof. n1 and n2 each represent a number of 0 or 1. X2 represents the above formula (2), the above formula (3), the above formula (4), or the above formula (0).)

[0141] Furthermore, the polymer (A) may also be a resin having a repeating structural unit containing at least one -C(=O)-O- group in the main chain and a repeating structural unit containing at least one hydroxyl group in the side chain as described in WO2020 / 026834, or a resin having a repeating structural unit containing at least one -C(=O)-O- group in the main chain and a repeating structural unit containing at least one hydroxyl group in the side chain.)

[0142] Furthermore, the polymer (A) may also be a copolymer having a repeating structural unit represented by the following formula (1-1) and a repeating structural unit represented by the following formula (1-2).

[0143]

Chemical 23

[0144]

[0145] (In formulae (1-1) and (1-2), R 1 and R 2 each independently represent a divalent organic group containing a linear, branched or cyclic functional group having 2 to 20 carbon atoms, and the organic group may also have at least one sulfur atom, nitrogen atom or oxygen atom. i and j each independently represent 0 or 1, and two Q's each represent a single bond, -O- group or -C(=O)-O- group. However, when both i and j are 0, at least one of the two Q's represents a -C(=O)-O- group.)

[0146] Furthermore, regarding the polymer (A), the contents of the polymers described in WO2022 / 196662, WO2009 / 008446, WO2011 / 074494, WO2013 / 018802, WO2020 / 026834, WO2022 / 071468 are all incorporated into this specification to the same extent as clearly described.

[0147] The polymer (A) may also have a structure represented by the following formula (E). The structure represented by formula (E) is located, for example, at the end (one end or both ends) of the polymer (A).

[0148]

Chemical 24

[0149]

[0150] (In formula (E), Y represents a monovalent group. n11 represents 0 or 1.)

[0151] Examples of the monovalent group in Y in formula (E) include monovalent organic groups having 1 to 30 carbon atoms.

[0152] Examples of Y in formula (E) include a monovalent residue obtained by removing one hydrogen atom from an aliphatic ring which may be substituted with a substituent, and a monovalent aromatic group which may be substituted with a substituent.

[0153] Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, etc.

[0154] As the aromatic group in the monovalent aromatic group which may also be substituted with substituents, for example, an aromatic hydrocarbon group can be mentioned. As the aromatic hydrocarbon group, for example, a phenyl group, a naphthyl group, an anthryl group, etc. can be mentioned.

[0155] As the compound represented by the formula (EA), for example, the following compounds can be mentioned.

[0156]

Chemical formula 25

[0157]

[0158]

Chemical formula 26

[0159]

[0160]

Chemical formula 27

[0161]

[0162]

Chemical formula 28

[0163]

[0164]

Chemical formula 29

[0165]

[0166]

Chemical formula 30

[0167]

[0168] There is no particular limitation on the molecular weight of the polymer (A).

[0169] The lower limit of the weight average molecular weight of the polymer (A) is, for example, 500, 1,000, 2,000, or 3,000.

[0170] The upper limit of the weight average molecular weight of the polymer (A) is, for example, 30,000, 20,000, or 10,000.

[0171] There is no particular limitation on the content of the polymer (A) in the composition for forming an underlayer film for a resist. From the viewpoint of obtaining the effects of the present invention well, it is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 95% by mass, and particularly preferably 65% by mass to 90% by mass with respect to the film constituent components.

[0172] In addition, in the present invention, the film constituent components refer to the components other than the solvent contained in the composition.

[0173] <Compound (B)>

[0174] Compound (B) is a compound having a hydrophobic substituent.

[0175] By adding the compound (B) to the composition for forming an underlayer film for a resist, the hydrophobicity of the underlayer film for a resist formed from the composition for forming an underlayer film for a resist can be improved.

[0176] In addition, the compound (B) has a structure different from that of the polymer (A).

[0177] There are no particular limitations on the hydrophobic substituents possessed by the compound (B). From the viewpoint of achieving the effects of the present invention well, an aryl group which may be substituted or an alkyl group having 1 to 10 carbon atoms which may be substituted is preferred.

[0178] Examples of the substituents in the aryl group which may be substituted include, for example, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, an RxOC(=O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having a total of 2 to 6 carbon atoms). etc.

[0179] Examples of the aryl group in the aryl group which may be substituted include, for example, a phenyl group, a naphthyl group, etc.

[0180] Examples of the substituents in the alkyl group having 1 to 10 carbon atoms which may be substituted include, for example, a hydroxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, a carboxyl group, etc.

[0181] In addition, although a hydroxyl group and a carboxyl group are hydrophilic groups, when the hydrophobic substituents as a whole are hydrophobic, the hydrophobic substituents may also have a hydrophilic group.

[0182] From the viewpoint of achieving the effects of the present invention well, the compound (B) preferably has at least one group represented by the following formula (X) as a hydrophobic substituent.

[0183]

Chemical formula 31

[0184]

[0185] (In formula (X), R 1 represents a monovalent group other than a hydrogen atom. n represents an integer of 0 to 5. When there are two or more Rs 1 , the two or more Rs 1 may be the same or different.)

[0186] Examples of R in formula (X) 1, for example, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, R x OC(=O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms in total.).

[0187] Compound (B) has a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0188]

Chemical Formula 32

[0189]

[0190] (In the formulas (Q-1) and (Q-2), * represents a connecting bond. X 1 represents a single bond, an oxygen atom or an alkylene group having 1 to 6 carbon atoms.).

[0191] From the viewpoint of well achieving the effects of the present invention, compound (B) is preferably a compound represented by the following formula (Y).

[0192]

Chemical Formula 33

[0193]

[0194] (In the formula (Y), X 1 represents an m-valent group.

[0195] R 11 represents a hydrophobic substituent.

[0196] L 1 represents a single bond or a divalent group.

[0197] m represents an integer of 1 to 4.

[0198] When there are two or more R 11 , the two or more R 11 may be the same or different.

[0199] When there are two or more L 1 , the two or more L 1 may be the same or different.).

[0200] As the hydrophobic substituent in the formula (Y) for R 11 , preferably an aryl group which may be substituted or an alkyl group having 1 to 10 carbon atoms which may be substituted.

[0201] Furthermore, as the hydrophobic substituent, preferably a group represented by the formula (X).

[0202] As L in formula (Y) 1 , for example, a divalent group represented by the following formula (L) can be exemplified.

[0203]

Chemical Formula 34

[0204]

[0205] (In formula (L), A 1 , A 2 and A 3 each independently represent a hydrogen atom, a methyl group or an ethyl group.

[0206] p represents an integer of 0 or 1.

[0207] *1 represents a bonding site bonded to R 11 in formula (Y).

[0208] *2 represents a bonding site bonded to X 1 in formula (Y).)

[0209] X in formula (Y) 1 , for example, has a ring structure. As the ring structure, for example, an aromatic ring, an aliphatic ring, a non-aromatic heterocyclic ring, etc. can be exemplified. As the aromatic ring, for example, a benzene ring, a naphthalene ring, etc. can be exemplified. As the aliphatic ring, for example, a cyclohexane ring, etc. can be exemplified. As the non-aromatic heterocyclic ring, for example, the ring structure represented by the said formula (Q-1) can be exemplified.

[0210] As X in formula (Y) 1 , for example, the following groups can be exemplified. In the following groups, * represents a bonding site.

[0211]

Chemical Formula 35

[0212]

[0213]

Chemical Formula 36

[0214]

[0215]

Chemical Formula 37

[0216]

[0217]

Chemical Formula 38

[0218]

[0219] From the viewpoint of well obtaining the effects of the present invention, compound (B) is preferably at least any one of the compound represented by the following formula (Y1) and the compound represented by the following formula (Y2).

[0220]

Chemical Formula 39

[0221]

[0222] (In formula (Y1), R 21 ~R 23 each independently represents a hydrophobic substituent.

[0223] In formula (Y2), R 31 ~R 34 each independently represents a hydrophobic substituent. X 1 represents a single bond, an oxygen atom, or an alkylene group having 1 to 6 carbon atoms.)

[0224] Examples of the compound (B) include the following compounds.

[0225]

Chemical Formula 40

[0226]

[0227]

Chemical Formula 41

[0228]

[0229]

Chemical Formula 42

[0230]

[0231]

Chemical Formula 43

[0232]

[0233] The compound represented by formula (Y) can be obtained, for example, by reacting the compound represented by the following formula (Y-1) with at least one of the compounds represented by the following formula (Y-2-1) and the following formula (Y-2-2).

[0234]

Chemical Formula 44

[0235]

[0236] (In formula (Y-1), X 1 represents an m-valent group.

[0237] A 1 、A 2 and A 3 each independently represents a hydrogen atom, a methyl group, or an ethyl group.

[0238] m represents an integer of 1 to 4.)

[0239]

Chemical Formula 45

[0240]

[0241] (In formula (Y-2-1), R 11 represents a hydrophobic substituent.

[0242] (p represents an integer of 0 or 1.))

[0243] As the R in formula (Y-2-1) 11 Among the hydrophobic substituents, preferably an aryl group which may be substituted, an alkyl group having 1 to 10 carbon atoms which may be substituted.

[0244] Furthermore, as the hydrophobic substituent, preferably a group represented by formula (X).

[0245]

Chemical formula 46

[0246]

[0247] (In formula (Y-2-2), R 12 represents a monovalent group other than a hydrogen atom. n represents an integer of 0 to 4. When there are two or more R 12 , two or more R 12 may be the same or different.))

[0248] As the R in formula (Y-2-2) 12 , for example, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, R x OC(=O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having a total of 2 to 6 carbon atoms.) etc.

[0249] As the compound represented by formula (Y-1), for example, the following compounds can be cited.

[0250]

Chemical formula 47

[0251]

[0252]

Chemical formula 48

[0253]

[0254]

Chemical formula 49

[0255]

[0256]

Chemical formula 50

[0257]

[0258] As the compound represented by formula (Y-2-1) and the compound represented by formula (Y-2-2), the following compounds can be exemplified, for example.

[0259]

Chemical Formula 51

[0260]

[0261]

Chemical Formula 52

[0262]

[0263]

Chemical Formula 53

[0264]

[0265] In addition, when the compound represented by formula (Y-2-1) has two or more carboxyl groups, when reacting the compound represented by formula (Y-1) with the compound represented by the following formula (Y-2-1), at least one carboxyl group in the compound represented by formula (Y-2-1) can also be capped by a solvent. As the solvent used for capping, alkylene glycol monoalkyl ethers can be exemplified, for example.

[0266] There is no particular limitation on the molecular weight of compound (B). For example, it is preferably 500 to 3,000.

[0267] The molecular weight of compound (B) is preferably smaller than the weight average molecular weight of polymer (A).

[0268] There is no particular limitation on the content of compound (B) in the resist underlayer film forming composition. From the viewpoint of achieving the effects of the present invention well, it is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, and particularly preferably 5% by mass to 20% by mass relative to polymer (A).

[0269] When the resist underlayer film forming composition contains a crosslinking agent (D), there is no particular limitation on the content of compound (B) in the resist underlayer film forming composition. It is preferably 3% by mass to 100% by mass, more preferably 5% by mass to 75% by mass, and particularly preferably 10% by mass to 50% by mass relative to crosslinking agent (D).

[0270] <Solvent (C)>

[0271] There is no particular limitation on solvent (C), and it can be water or an organic solvent.

[0272] As the organic solvent, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, etc. can be exemplified, for example.

[0273] As the alkylene group of the alkylene glycol monoalkyl ether, for example, an alkylene group having 2 to 4 carbon atoms can be mentioned.

[0274] As the alkyl group of the alkylene glycol monoalkyl ether, for example, an alkyl group having 1 to 4 carbon atoms can be mentioned.

[0275] As the number of carbon atoms of the alkylene glycol monoalkyl ether, for example, 3 to 8 can be mentioned.

[0276] As the alkylene glycol monoalkyl ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. can be mentioned.

[0277] As the alkylene group of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether, for example, an alkylene group having 2 to 4 carbon atoms can be mentioned.

[0278] As the alkyl group of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether, for example, an alkyl group having 1 to 4 carbon atoms can be mentioned.

[0279] As the mono-carboxylic acid of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether, a saturated mono-carboxylic acid having 2 to 4 carbon atoms can be mentioned.

[0280] As the saturated mono-carboxylic acid having 2 to 4 carbon atoms, for example, acetic acid, propionic acid, butyric acid can be mentioned.

[0281] As the number of carbon atoms of the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether, for example, 5 to 10 can be mentioned.

[0282] As the mono-carboxylic acid ester of the alkylene glycol monoalkyl ether, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc. can be mentioned.

[0283] As other organic solvents, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. can be mentioned.

[0284] Among these solvents (C), alkylene glycol monoalkyl ether and mono-carboxylic acid ester of alkylene glycol monoalkyl ether are preferred.

[0285] These solvents (C) can be used alone or in combination of two or more.

[0286] The mass ratio of the organic solvent in the solvent (C) is not particularly limited, and is preferably 50% by mass to 100% by mass.

[0287] The content of the solvent (C) in the composition for forming an underlayer film of a resist is not particularly limited, and 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.

[0288] <Crosslinking agent (D)>

[0289] There is no particular limitation on the crosslinking agent (D).

[0290] The crosslinking agent (D) has a structure different from that of the polymer (A) and the compound (B).

[0291] As the crosslinking agent (D), an amino plastic crosslinking agent or a phenolic plastic crosslinking agent is preferably used.

[0292] The amino plastic crosslinking agent is an addition condensate of a compound having an amino group such as melamine or guanamine and formaldehyde.

[0293] The phenolic plastic crosslinking agent refers to an addition condensate of a compound having a phenolic hydroxyl group and formaldehyde.

[0294] As the crosslinking agent (D), for example, a compound having two or more of the following structures can be cited.

[0295]

Chemical formula 54

[0296]

[0297] (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 linking bond.)

[0298] The linking bond is bonded to, for example, a nitrogen atom, a carbon atom constituting an aromatic hydrocarbon ring, or the like.

[0299] As R 101 is preferably a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure.

[0300]

Chemical formula 55

[0301]

[0302] (In the structure, R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a linking bond.)

[0303] As the crosslinking agent (D), a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxyl group is preferred. These may be used alone or in combination of two or more.

[0304] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylol melamine are acyloxymethylated or a mixture thereof, and the like.

[0305] Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol guanamine are methoxymethylated or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxy guanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol guanamine are acyloxymethylated or a mixture thereof, and the like.

[0306] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof, and the like.

[0307] Furthermore, as the glycoluril compound, a glycoluril derivative represented by the following formula (1E) may also be used.

[0308]

Chemical Formula 56

[0309]

[0310] (In formula (1E), each of the four R1 independently represents 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.)

[0311] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formula (1E-1) to formula (1E-6).

[0312]

Chemical Formula 57

[0313]

[0314] The glycoluril derivative represented by the formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0315]

Chemical Formula 58

[0316]

[0317] (In formula (2E), each of R2 and R3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and each of R4 independently represents an alkyl group having 1 to 4 carbon atoms.)

[0318]

Chemical Formula 59

[0319]

[0320] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0321] Examples of the glycoluril derivative represented by the formula (2E) include compounds represented by the following formula (2E-1) to formula (2E-4). Further, examples of the compound represented by the formula (3d) include compounds represented by the following formula (3d-1) and formula (3d-2).

[0322]

Chemical Formula 60

[0323]

[0324] Examples of the urea compound include, for example, tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolurea are methoxymethylated or a mixture thereof, tetramethoxyethylurea, and the like.

[0325] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (G-1) or formula (G-2).

[0326]

Chemical Formula 62

[0327]

[0328] (In formula (G-1) and formula (G-2), Q 1 represents a single bond or an m1-valent organic group.)

[0329] R 1 and R 4 each independently represent an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms.)

[0330] R 2 and R 5 each independently represent a hydrogen atom or a methyl group.)

[0331] R 3 and R 6 each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.)

[0332] n1 represents an integer where 1 ≤ n1 ≤ 3, n2 represents an integer where 2 ≤ n2 ≤ 5, n3 represents an integer where 0 ≤ n3 ≤ 3, n4 represents an integer where 0 ≤ n4 ≤ 3, and 3 ≤ (n1 + n2 + n3 + n4) ≤ 6 is an integer.

[0333] n5 represents an integer where 1 ≤ n s ≤ 3, n6 represents an integer where 1 ≤ n6 ≤ 4, n7 represents an integer where 0 ≤ n7 ≤ 3, n8 represents an integer where 0 ≤ n8 ≤ 3, and 2 ≤ (n5 + n6 + n7 + n8) ≤ 5 is an integer.

[0334] m1 represents an integer from 2 to 10. )

[0335] Furthermore, as the compound having a phenolic hydroxyl group, compounds represented by the following formula (G-3) or formula (G-4) can be exemplified.

[0336] The compound represented by formula (G-1) or formula (G-2) can also be a product obtained by reacting the compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0337]

Chemical Formula 63

[0338]

[0339] (In formula (G-3) and formula (G-4), Q 2 represents a single bond or an m2-valent organic group.

[0340] R 8 、R 9 、R 11 and R 12 each represent a hydrogen atom or a methyl group.

[0341] 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.

[0342] n9 represents an integer where 1 ≤ n9 ≤ 3, n10 represents an integer where 2 ≤ n10 ≤ 5, n 11 represents an integer where 0 ≤ n 11 ≤ 3, n 12 represents an integer where 0 ≤ n 12 ≤ 3, and 3 ≤ (n9 + n 10 + n 11 + n 12 ) ≤ 6 is an integer.

[0343] n 13 represents an integer where 1 ≤ n 13 ≤ 3, n 14 represents an integer where 1 ≤ n 14An integer less than or equal to 4, n 15 represents 0 ≤ n 15 An integer less than or equal to 3, n 16 represents 0 ≤ n 16 An integer less than or equal to 3, 2 ≤ (n 13 + n 14 + n 15 + n 16 ) ≤ 5.

[0344] m2 represents an integer from 2 to 10. )

[0345] As Q 2 in the m2-valent organic group, examples include m2-valent organic groups having 1 to 4 carbon atoms.

[0346] As the compound represented by formula (G-1) or formula (G-2), examples include the following compounds.

[0347]

Chemical formula 64

[0348]

[0349]

Chemical formula 65

[0350]

[0351]

Chemical formula 66

[0352]

[0353]

Chemical formula 67

[0354]

[0355]

Chemical formula 68

[0356]

[0357] As the compound represented by formula (G-3) or formula (G-4), examples include the following compounds.

[0358]

Chemical formula 69

[0359]

[0360]

Chemical formula 70

[0361]

[0362] The above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd. Examples of products include the trade name TMOM-BP of Asahi Organic Materials Industry Co., Ltd.

[0363] Among these, glycoluril compounds are preferred, and specifically, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 of the hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, compounds in which 1 to 4 of the hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof are preferred, and further, tetramethoxymethyl glycoluril is preferred.

[0364] There is no particular limitation on the molecular weight of the crosslinking agent (D), and it is preferably 500 or less.

[0365] There is no particular limitation on the content of the crosslinking agent (D) in the composition for forming an underlayer film of a resist. Relative to the polymer (A), for example, it is 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass.

[0366] <Curing catalyst (E)>

[0367] As the curing catalyst (E) contained as an optional component of the composition for forming an underlayer film of a resist, either a thermal acid generator or a photoacid generator can be used, and a thermal acid generator is preferably used.

[0368] Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium phenolsulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium p-benzenesulfonate), 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-toluenesulfonate, N-methylmorpholine p-hydroxybenzenesulfonate, and N-methylmorpholine 5-sulfosalicylic acid.

[0369] Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0370] Examples of the onium salt compounds include 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.

[0371] Examples of the sulfimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalimide, and the like.

[0372] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0373] The curing catalyst (E) may be used alone or in combination of two or more.

[0374] When the curing catalyst (E) is used, the content ratio of the curing catalyst (E) is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, relative to the crosslinking agent (D).

[0375] <Other components>

[0376] In order to prevent the occurrence of pinholes, streaks, etc. and further improve the coatability on an uneven surface, a surfactant may be further added to the composition for forming the underlayer film of the resist.

[0377] Examples of the surfactant include nonionic surfactants such as 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; fluorine-based surfactants such as EFTOEF301, EF303, EF352 (manufactured by Tochem 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, Surflon 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.).

[0378] 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 the anti-reflective film underlayer.

[0379] These surfactants can be added alone or in combination of two or more kinds.

[0380] The solid components contained in the composition for forming the anti-reflective film underlayer of the present invention, that is, the components excluding the solvent, are, for example, 0.01% by mass to 10% by mass.

[0381] The water contact angle of the anti-reflective film underlayer formed from the composition for forming the anti-reflective film underlayer is, for example, 40° to 80°, 45° to 75°, or 50° to 70°.

[0382] The anti-reflective film underlayer is, for example, an anti-reflective film underlayer having a film thickness of 5 nm when the composition for forming the anti-reflective film underlayer is coated on a silicon wafer and baked at 205°C for 60 seconds.

[0383] The water contact angle can be determined by the droplet method using, for example, a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.).

[0384] (Anti-reflective film underlayer)

[0385] The underlayer film of the resist of the present invention is a cured product of the composition for forming the underlayer film of the resist.

[0386] The underlayer film of the resist can be produced, for example, by applying the composition for forming the underlayer film of the resist onto a semiconductor substrate and then baking it.

[0387] Examples of the semiconductor substrate onto which the composition for forming the underlayer film of the resist is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0388] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed, for example, by an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, a vacuum evaporation method, or a spin-on-glass (SOG) method. Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (boro-phospho-silicate glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0389] On such a semiconductor substrate, the composition for forming the underlayer film of the resist of the present invention is applied by an appropriate coating method such as a spinner or a coater. Thereafter, the underlayer film of the resist is formed by baking using a heating method such as a hot plate. 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.

[0390] The water contact angle of the underlayer film of the resist is, for example, 40° to 80°, 45° to 75°, or 50° to 70°.

[0391] The water contact angle can be obtained, for example, by the droplet method using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.).

[0392] The film thickness of the underlayer film for resist 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 (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).

[0393] The method for measuring the film thickness of the underlayer film for resist in this specification is as follows.

[0394] · Name of measuring device: Ellipsometric film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0395] · SWE (Single Wavelength Ellipsometer) mode

[0396] · Arithmetic mean of 8 points (for example, measuring 8 points at intervals of 1 cm in the X direction of the wafer)

[0397] (Laminate)

[0398] The laminate of the present invention includes a semiconductor substrate and the underlayer film for resist of the present invention.

[0399] Examples of the semiconductor substrate include the semiconductor substrates described above.

[0400] The underlayer film for resist is disposed, for example, on the semiconductor substrate.

[0401] (Method for manufacturing a semiconductor device, method for forming a pattern)

[0402] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0403] · 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

[0404] A step of forming a resist film on the underlayer film for resist.

[0405] The pattern forming method of the present invention at least includes the following steps.

[0406] A step of forming an underlayer resist film on a semiconductor substrate using the composition for forming an underlayer resist film of the present invention,

[0407] A step of forming a resist film on the underlayer resist film,

[0408] A step of irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern, and

[0409] A step of etching the underlayer resist film using the resist pattern as a mask.

[0410] Generally, a resist layer is formed on the underlayer resist film.

[0411] 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. Further, 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.

[0412] As the resist formed on the underlayer resist film by a known method (for example, coating and baking of a resist composition), there is no particular limitation as long as it reacts to the light or electron beam (EB) used for irradiation. Either a negative photoresist or a positive photoresist can be used.

[0413] In addition, in this specification, a resist that reacts to EB is also referred to as a photoresist.

[0414] Examples of photoresists include: positive photoresists formed from novolak resins and 1,2-naphthoquinone diazide sulfonates; chemically amplified photoresists formed from a binder having a group that decomposes by acid to increase the alkali dissolution rate and a photoacid generator; chemically amplified photoresists formed from a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists formed from a binder having a group that decomposes by acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; resists containing metal elements, etc. Specific examples 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.). Additionally, examples include fluorine atom-containing polymer-based photoresists such as those described in Proc. SPIE, Vol. 3999, 330 - 334 (2000), Proc. SPIE, Vol. 3999, 357 - 364 (2000), and Proc. SPIE, Vol. 3999, 365 - 374 (2000).

[0415] Furthermore, so-called resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution pattern compositions based on organometallic solutions 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. can be used, but are not limited thereto.

[0416] Examples of the resist composition include the following compositions.

[0417] A photoactive or radiation-sensitive resin composition comprising a resin A having a repeating unit and a compound represented by the following general formula (121), wherein the repeating unit has an acid-decomposable group having a polar group protected by a protecting group that is cleaved by the action of an acid.

[0418] [Chemical 71]

[0419]

[0420] In the general formula (121), m represents an integer of 1 to 6.

[0421] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0422] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0423] L2 represents an alkylene group which may have a substituent or a single bond.

[0424] W1 represents a cyclic organic group which may have a substituent.

[0425] M + represents a cation.

[0426] 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 Groups 3 to 15 and Periods 3 to 7 of the Periodic Table.

[0427] A radiation-sensitive resin composition comprising a polymer having 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), and an acid generator.

[0428] [Chemical 72]

[0429]

[0430] (In the 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 hydrogen sulfide 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 the 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. R4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)

[0431] 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.

[0432]

Chemical formula 73

[0433]

[0434] [In the formula, R 2 represents an alkyl group having 1 to 6 carbon atoms which may also have a halogen atom, a hydrogen atom or a halogen atom, and X 1 represents a single bond, -CO-O-*, or -CO-NR 4 -*, * represents a bonding bond 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 also have one or more groups selected from a hydroxyl group and a carboxyl group.]

[0435] As the resist film, the following can be exemplified.

[0436] A resist film containing a base resin, the base resin containing a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.

[0437]

Chemical formula 74

[0438]

[0439] (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 from 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.)

[0440] As the resist material, the following resist materials can be exemplified.

[0441] A resist material containing a polymer having a repeating unit represented by the following formula (b1) or formula (b2).

[0442]

Chemical formula 75

[0443]

[0444] (In formulas (b1) and (b2), 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. Part of the methylene groups constituting the alkylene group may also be replaced by an ether group, an ester group or a group containing a lactone ring. Furthermore, at least one hydrogen atom contained in X 2 is replaced by 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. Part of the methylene groups constituting the alkylene group may also be replaced by an ether group or an ester group. Rf 1 ~Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, and at least one is a fluorine atom or a trifluoromethyl group. Furthermore, Rf 1 and Rf 2 may also combine to form a carbonyl group. R 1 ~R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aryloxyalkyl group having 7 to 12 carbon atoms. Part or all of the hydrogen atoms of these groups may also be replaced by a hydroxyl group, a carboxyl group, a halogen atom, a side oxygen group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group or a group containing a sulfonium salt. Part of the methylene groups constituting these groups may also be replaced by an ether group, an ester group, a carbonyl group, a carbonate group or a sulfonate group. Furthermore, R 1 and R 2 may bond to form a ring together with the sulfur atom to which they are bonded.)

[0445] A resist material containing a base resin, the base resin containing a polymer having a repeating unit represented by the following formula (a).

[0446] [Chemical 76]

[0447]

[0448] (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 1is a single bond, a phenylene group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms which may also 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.)

[0449] A resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid,

[0450] contains a substrate component (A) which changes its solubility in a developer by the action of an acid, and a fluorine additive component (F) which exhibits decomposability in an alkaline developer,

[0451] The fluorine additive component (F) contains a fluororesin component (F1), and the 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).

[0452]

Chemical formula 77

[0453]

[0454] [In formula (f2-r-1), Rf 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n” is an integer of 0 to 2. * is a linking bond.]

[0455] The structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0456]

Chemical formula 78

[0457]

[0458] [In 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 which may have a substituent. X 01 is a single bond or a divalent linking group. R 2 are each independently an organic group having a fluorine atom.]

[0459] Examples of coatings, coating solutions, and coating compositions include the following.

[0460] A coating containing a metal oxo-hydroxo network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0461] An inorganic oxygen / hydroxyl group-containing composition.

[0462] 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; and the hydrolyzable metal compound is 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).

[0463] 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 is 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.

[0464] An aqueous solution of an inorganic pattern-forming precursor, which is a mixture comprising water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0465] Irradiation with light or an electron beam is carried out, for example, through a mask for forming a predetermined pattern. For example, i-ray, 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 according to the present invention is preferably suitable for irradiation with EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm), and more preferably suitable for EUV (extreme ultraviolet) exposure.

[0466] There are no particular limitations on the irradiation energy for an electron beam and the exposure amount of light.

[0467] After irradiation with light or an electron beam and before development, baking (PEB: PostExposure Bake) may also be carried out.

[0468] There is no particular limitation on the baking temperature, which is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0469] There is no particular limitation on the baking time, which is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0470] For development, an alkaline developer can be used, for example.

[0471] Examples of the development temperature include 5°C to 50°C.

[0472] Examples of the development time include 10 seconds to 300 seconds.

[0473] As the alkaline developer, aqueous solutions of bases such as inorganic bases like 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 above aqueous solutions of bases for use. Among these, an aqueous solution of a quaternary ammonium salt is preferably used as the developer, and more preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Further, a surfactant or the like can also be added to these developers. It is also possible to use an organic solvent such as butyl acetate instead of the alkaline developer for development, and a method of developing the portion of the photoresist where the alkali dissolution rate is not increased.

[0474] Next, the formed resist pattern is used as a mask to etch the underlying resist film. The etching can be dry etching or wet etching, and dry etching is preferred.

[0475] 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. After that, through the step of processing the semiconductor substrate by a known method (such as dry etching method), semiconductor components can be manufactured.

[0476] Examples

[0477] Next, the content of the present invention will be specifically described by way of examples, but the present invention is not limited by them.

[0478] <Measurement of molecular weight>

[0479] The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 in the present specification are the measurement results by gel permeation chromatography (hereinafter simply referred to as GPC). The measurement was carried out using a GPC device manufactured by Tosoh Corporation, and the measurement conditions were as follows.

[0480] · GPC column: TSKgel Super-Multipore HZ-N (2 columns)

[0481] · Column temperature: 40 °C

[0482] · Solvent: Tetrahydrofuran (THF)

[0483] · Flow rate: 0.35 ml / min

[0484] · Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0485] <Synthesis Example 1>

[0486] 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 4.76 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 45.68 g of propylene glycol monomethyl ether 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 1. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 1 in terms of standard polystyrene was 5,400, and the dispersity was 3.4. The structure present in Polymer 1 is shown by the following formula.

[0487]

Chemical Formula 79

[0488]

[0489] <Synthesis Example 2>

[0490] 5.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 3.39 g of 5-nitroisophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.64 g of 4-tert-butylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.46 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 22.11 g of propylene glycol monomethyl ether 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 weight-average molecular weight of the obtained Polymer 2 in terms of standard polystyrene was 3,800, and the dispersity was 2.5. The structure present in Polymer 2 is shown by the following formula.

[0491]

Chemical Formula 80

[0492]

[0493] <Synthesis Example 3>

[0494] 4.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 6.65 g of 2,4,6-trimethylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 26.03 g of propylene glycol monomethyl ether 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 3. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 3 in terms of standard polystyrene was 690, and the dispersity was 1.0. The structure present in Polymer 3 is shown by the following formula.

[0495]

Chemical Formula 81

[0496]

[0497] <Synthesis Example 4>

[0498] 4.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 7.22 g of 4-tert-butylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 27.36 g of propylene glycol monomethyl ether 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 4. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 4 in terms of standard polystyrene was 910, and the dispersity was 1.0. The structure present in Polymer 4 is shown by the following formula.

[0499]

Chemical Formula 82

[0500]

[0501] <Synthesis Example 5>

[0502] 3.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 7.11 g of 4-(heptyloxy)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.38 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 24.49 g of propylene glycol monomethyl ether 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 5. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 5 in terms of standard polystyrene was 1,200 and the dispersity was 1.0. The structure present in Polymer 5 is shown by the following formula.

[0503]

Chemical Formula 83

[0504]

[0505] <Synthesis Example 6>

[0506] 3.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 5.77 g of 4-(trifluoromethyl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.38 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 21.36 g of propylene glycol monomethyl ether 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 6. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 6 in terms of standard polystyrene was 890 and the dispersity was 1.0. The structure present in Polymer 6 is shown by the following formula.

[0507]

Chemical Formula 84

[0508]

[0509] <Synthesis Example 7>

[0510] 4.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 10.45 g of 3,5-bis(trifluoromethyl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 34.90 g of propylene glycol monomethyl ether 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 7. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 7 in terms of standard polystyrene was 1030 and the dispersity was 1.0. The structure present in Polymer 7 is shown by the following formula.

[0511]

Chemical Formula 85

[0512]

[0513] <Synthesis Example 8>

[0514] 5.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 13.80 g of 3,5-di-tert-butyl-4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.64 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 19.43 g of propylene glycol monomethyl ether 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 8. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 8 in terms of standard polystyrene was 1,060, and the dispersity was 1.2. The structure present in Polymer 8 is shown by the following formula.

[0515]

Chemical Formula 86

[0516]

[0517] <Synthesis Example 9>

[0518] 2.00 g of 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid (product name: TEPIC-SS, manufactured by Nissan Chemical Industries, Ltd.), 9.39 g of tetrabromophthalic anhydride (manufactured by Modorikagaku Co., Ltd.), and 0.26 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 27.16 g of propylene glycol monomethyl ether 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 9. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained Polymer 9 in terms of standard polystyrene was 910, and the dispersity was 1.0. The structure present in Polymer 9 is shown by the following formula.

[0519]

Chemical Formula 87

[0520]

[0521] <Synthesis Example 10>

[0522] 2.00 g of the product name EPICLON HP-4700 (manufactured by DIC Corporation), 3.41 g of 3,5-di-tert-butyl-4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.16 g of tetrabutylphosphonium bromide (manufactured by Kitakyo Chemical Industry Co., Ltd.) were added to 5.56 g of propylene glycol monomethyl ether 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 10. GPC analysis was performed, and as a result, the weight-average molecular weight of the obtained polymer 10 in terms of standard polystyrene was 2,010, and the dispersity was 1.6. The structure present in polymer 10 is shown by the following formula.

[0523] [Chemical Formula 88]

[0524]

[0525] [Comparative Synthesis Example 1]

[0526] 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the reaction vessel with nitrogen, the reaction was carried out at 130 °C for 24 hours to obtain a solution containing 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 6,800, and the dispersity was 4.8. The structure present in comparative polymer 1 is shown by the following formula.

[0527] [Chemical Formula 89]

[0528]

[0529] (Preparation of the composition for forming the lower layer film of the resist)

[0530] (Examples, Comparative Examples)

[0531] The polymers, crosslinking agents, curing catalysts, and solvents obtained in the above Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 were mixed in the ratios shown in Tables 1-1 and 1-2 so that the solid content was about 0.19% by mass, and the compositions for forming the lower layer film of the resist were respectively prepared by filtering through a 0.1-μm fluororesin filter.

[0532] The meanings of the abbreviations in Tables 1-1 and 1-2 are as follows.

[0533] ·PL-LI: tetramethoxymethyl glycoluril

[0534] · PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, tetrahydro-1,3,4,6-tetra[(2-methoxy-1-methylethoxy)methyl]-(the following structural formula)

[0535]

Chemical Formula 90

[0536]

[0537] · PyPSA: Pyridinium-p-hydroxybenzenesulfonic acid

[0538] · R-30N: Surfactant (manufactured by DIC Corporation)

[0539] · PGMEA: Propylene glycol monomethyl ether acetate

[0540] · PGME: Propylene glycol monomethyl ether

[0541] The addition amounts are expressed in parts by mass, and the solvent is expressed as a composition ratio.

[0542] Table 1-1

[0543]

[0544] Table 1-2

[0545]

[0546] (Dissolution test of the photoresist solvent)

[0547] The compositions for forming the lower resist film of Examples 1 to 10, Comparative Example 1, and Comparative Example 2 were respectively coated on a silicon wafer using a spin coater. This silicon wafer was baked on a hot plate at 205 °C for 60 seconds to obtain a film with a thickness of 5 nm. These lower resist films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (mass ratio) used as a photoresist solvent, and when the film thickness change was the following case was set as "good", and when it exceeded it was set as "bad", and the results are shown in Table 2.

[0548] Table 2

[0549] Dissolution test Example 1 Good Example 2 Good Example 3 Good Example 4 Good Example 5 Good Example 6 Good Example 7 Good Example 8 Good Example 9 Good Example 10 Good Comparative Example 1 Good Comparative Example 2 Good

[0550] (Measurement of water contact angle)

[0551] It was confirmed whether the surface hydrophobicity of the lower resist film was improved by adding a hydrophobic additive through the measurement of the water contact angle.

[0552] The resist underlayer film-forming compositions of Examples 1 to 10 and Comparative Example 2 were each applied to a silicon wafer using a spin coater. This silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. The water contact angles of these resist underlayer films were measured by the droplet method using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 3.

[0553] Table 3

[0554] Contact angle (°) Example 1 57 Example 2 64 Example 3 66 Example 4 62 Example 5 68 Example 6 56 Example 7 62 Example 8 54 Example 9 63 Example 10 69 Comparative Example 2 50

[0555] It was confirmed that the contact angle increased by the addition of the hydrophobic additive.

[0556] From this, it was confirmed that the hydrophobicity of the surface of the resist underlayer film was improved by the addition of the hydrophobic additive.

[0557] (Resist pattern evaluation)

[0558] [Formation test of resist patterns by an electron beam lithography apparatus]

[0559] The resist underlayer film-forming compositions of Examples 1 to 10, Comparative Example 1, and Comparative Example 2 were each applied to a silicon wafer using a spin coater. This silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a thickness of 5 nm. On this resist underlayer film, a positive resist solution for EUV was spin-coated and heated at 105°C for 60 seconds to form an EUV resist film. This resist film was exposed using an electron beam lithography apparatus (ELS-G130) under predetermined conditions. After exposure, it was baked at 95°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and 2.38% aqueous tetramethylammonium hydroxide solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) was used as a photoresist developer for 30 seconds of puddle development. Resist patterns with line sizes of 18 nm to 32 nm were formed. The length of the resist patterns was measured using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100).

[0560] Regarding the photoresist patterns obtained in this way, formation of 28 nm line and space (L / S) was carried out. It was confirmed that 28 nm L / S patterns were formed in all cases of Examples 1 to 10. Furthermore, the charge amount of the formation of 28 nm line / 56 nm pitch (line and space (L / S = 1 / 1)) was taken as the most preferable irradiation energy, and the irradiation energy at this time (μC / cm 2) The minimum CD (Critical Dimension) size and LWR (Line Width Roughness) where no collapse was observed within the exposure shot area of the resist pattern are shown in Table 4. It was confirmed that the optimum exposure energy was reduced in Examples 1 to 10 compared to Comparative Example 2. Furthermore, it was confirmed that the minimum CD size was increased and the LWR was reduced in Examples 1 to 10 compared to Comparative Example 1.

[0561] Table 4

[0562]

Claims

1. A composition for forming an underlayer film of a resist, comprising a polymer (A), a compound (B) having a hydrophobic substituent, and a solvent (C).

2. The composition for forming an underlayer film of a resist according to claim 1, wherein the polymer (A) is at least any one of an isocyanuric acid-based polymer, a polyester-based polymer, an acrylic acid-based polymer, and a polyether.

3. The composition for forming an underlayer film of a resist according to claim 1, wherein the polymer (A) is a polymer having a hydroxyl group in the unit structure.

4. The composition for forming an underlayer film of a resist according to claim 1, wherein the hydrophobic substituent of the compound (B) is a substitutable aryl group or a substitutable alkyl group having 1 to 10 carbon atoms.

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

6. The composition for forming an underlayer film of a resist according to claim 1, further comprising a crosslinking agent (D).

7. The composition for forming an underlayer film of a resist according to claim 6, wherein the crosslinking agent (D) is at least one selected from aminoplast crosslinking agents and phenolic plastic crosslinking agents.

8. The composition for forming an underlayer film of a resist according to claim 1, further comprising a curing catalyst (E).

9. 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 8.

10. A laminate, comprising a semiconductor substrate and the underlayer film of a resist according to claim 9.

11. A method for manufacturing a semiconductor device, comprising: 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 8, and a step of forming a resist film on the underlayer film of a resist.

12. A pattern forming method, comprising: 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 8, a step of forming a resist film on the underlayer film of a resist, a step of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, and a step of etching the underlayer film of a resist using the resist pattern as a mask.

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