Resist underlayer film-forming composition for reducing environmental burden

Abstract

A composition for forming a resist underlayer film, the composition containing a first component, a second component, and a solvent, the second component being a water-soluble polymer, the mass ratio of the first component to the second component (first component: second component) being 99: 1 to 50: 50, and the solvent containing 50 mass% or more of water relative to the solvent.

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method. Background Art

[0002] In the manufacture of semiconductor devices, microfabrication has been performed by photolithography using a photoresist composition. The microfabrication is a method in which a thin film of the photoresist composition is formed on a silicon wafer, active energy rays such as ultraviolet rays are irradiated thereon through a mask pattern on which a pattern of the semiconductor device is drawn, and development is performed, and the silicon wafer is etched using the obtained resist pattern as a protective film.

[0003] However, in recent years, with the development of high integration of semiconductor devices, the active energy rays used have also tended to be shortened from KrF excimer laser (248nm) to ArF excimer laser (193nm). Along with this, diffuse reflection of active energy rays from the substrate and the influence of standing waves are great problems. Therefore, the method of setting an anti-reflective film (Bottom Anti-Reflective Coating: BARC) as a resist bottom layer between the photoresist and the substrate has been gradually and widely studied.

[0004] For example, the inventors of the present application have proposed a composition for forming an anti-reflective film that can be used to obtain the following anti-reflective film for lithography, wherein the anti-reflective film for lithography has a high effect of preventing reflected light, does not mix with the resist layer, can obtain an excellent resist pattern and a wider focus margin depth, and has a dry etching speed greater than that of the resist (see Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2003 / 017002 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The resist underlayer film-forming composition is generally an organic solvent-based composition obtained by dissolving a polymer in an organic solvent.

[0010] Considering the impact of volatile organic solvents on the environment and the health of workers who handle paints, the replacement of organic solvent-based paints with water-based paints is being actively studied.

[0011] The resist underlayer film-forming composition is used in a clean room, so the volatile organic solvent is not easily released into the environment, and workers are not exposed to the organic solvent.

[0012] However, from the viewpoint of waste liquid treatment and the fact that organic solvent-based compositions are flammable and require caution in handling and transportation, aqueous compositions are preferred.

[0013] An object of the present invention is to provide a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method using water as a solvent.

[0014] Means for solving problems

[0015] The inventors of the present application have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, thereby completing the present invention having the following gist.

[0016] That is, the present invention includes the following contents.

[0017] [1] A resist underlayer film-forming composition comprising a first component, a second component and a solvent,

[0018] The second component is a water-soluble polymer,

[0019] The mass ratio of the first component to the second component (first component: second component) is 99:1 to 50:50,

[0020] The solvent contains 50% by mass or more of water based on the solvent.

[0021] [2] A resist underlayer film-forming composition comprising a first component and a solvent,

[0022] The first component is a compound including at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2),

[0023] The solvent contains 50% by mass or more of water based on the solvent.

[0024]

[0025] (In the formula (1), X1 represents a group represented by any one of the following formulae (1-1) to (1-4). Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (1-5).

[0026] In formula (2), Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.

[0027]

[0028] (In formulas (1-1) to (1-3), R1 to R5 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, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms. R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0029] In the formula (1-4), Z3 represents a single bond or a divalent group represented by the following formula (1-5).

[0030] * represents a connecting bond. *1 represents a connecting bond bonded to a carbon atom in formula (1). *2 represents a connecting bond bonded to a nitrogen atom in formula (1).

[0031]

[0032] (In formula (1-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a connecting bond to the nitrogen atom in formula (1) or formula (1-4). *4 represents a connecting bond.)

[0033] [3] The resist underlayer film forming composition according to [1], wherein the first component is a compound containing at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2).

[0034]

[0035] (In the formula (1), X1 represents a group represented by any one of the following formulae (1-1) to (1-4). Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (1-5).

[0036] In formula (2), Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.

[0037]

[0038] (In formulas (1-1) to (1-3), R1 to R5 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, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms. R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0039] In the formula (1-4), Z3 represents a single bond or a divalent group represented by the following formula (1-5).

[0040] * represents a connecting bond. *1 represents a connecting bond bonded to a carbon atom in formula (1). *2 represents a connecting bond bonded to a nitrogen atom in formula (1).

[0041]

[0042] (In formula (1-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a connecting bond to the nitrogen atom in formula (1) or formula (1-4). *4 represents a connecting bond.)

[0043] [4] The resist underlayer film forming composition according to [2] or [3], wherein Q1 is represented by the following formula (2-1).

[0044]

[0045] (In formula (2-1), Q 11 represents a divalent organic group represented by any one of the following formulae (2-1-1) to (2-1-4). n1 and n2 each independently represent 0 or 1. * represents a connecting bond. )

[0046]

[0047] (In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a connecting bond.

[0048] In formula (2-1-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 21 When there are 2 or more R 21 It can be the same or different.

[0049] In formula (2-1-2), Z4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. 22 When there are 2 or more R 22 Can be the same or different. 23 When there are 2 or more R 23 It can be the same or different.

[0050] In formula (2-1-3), n14 represents an integer of 0 to 4. 24 When there are 2 or more R 24 It can be the same or different.

[0051] In formula (2-1-4), Z5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. 25 When there are 2 or more R 25 Can be the same or different. 26 When there are 2 or more R 26 Can be the same or different.)

[0052] [5] The resist underlayer film forming composition according to any one of [1] to [3], wherein the first component contains at least one of a structure represented by the following formula (E-1) and a structure represented by the following formula (E-2).

[0053]

[0054] (In formula (E-1) and formula (E-2), * represents a connecting bond.)

[0055] [6] The resist underlayer film forming composition according to [2], comprising a second component, wherein the second component is a water-soluble polymer.

[0056] [7] The resist underlayer film-forming composition according to [1] or [6], wherein the water-soluble polymer is at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid, and water-soluble cellulose.

[0057] [8] The aqueous composition for forming a resist underlayer film according to [6] or [7], wherein a mass ratio of the first component to the second component (first component:second component) is 99:1 to 50:50.

[0058] [9] The resist underlayer film-forming composition according to any one of [1] to [8], further comprising a crosslinking agent.

[0059]

[10] The resist underlayer film forming composition according to any one of [1] to [9], further comprising a curing catalyst.

[0060]

[11] A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to any one of [1] to

[10] .

[0061]

[12] A semiconductor processing substrate comprising:

[0062] semiconductor substrate, and

[0063]

[11] The resist underlayer film described.

[0064]

[13] A method for manufacturing a semiconductor device, comprising the following steps:

[0065] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as described in any one of [1] to

[10] ; and

[0066] A step of forming a resist film on the resist underlayer film.

[0067]

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

[0068] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to

[10] ;

[0069] forming a resist film on the resist underlayer film;

[0070] a step of irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and

[0071] A step of etching the resist underlayer film using the resist pattern as a mask.

[0072] Effects of the Invention

[0073] According to the present invention, a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for manufacturing a semiconductor element, and a pattern forming method using water as a solvent can be provided, which can reduce the amount of organic solvents used in the art in the past, and can help reduce environmental load. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] [ Figure 1 ] Figure 1 This is a SEM photograph of a formation example of a resist pattern. DETAILED DESCRIPTION

[0075] (Resist underlayer film forming composition)

[0076] One embodiment of the resist underlayer film forming composition of the present invention contains a first component and water.

[0077] One embodiment of the resist underlayer film-forming composition of the present invention contains a first component, a second component, and water.

[0078] <1st ingredient>

[0079] The first component is an organic compound.

[0080] The first component is a component that can be used together with the second component in the resist underlayer film-forming composition, for example. In order to use the resist underlayer film-forming composition, the first component is an organic compound that is soluble in the above-mentioned solvent.

[0081] The molecular weight of the first component is not particularly limited, and the first component may be a low molecular weight compound or a high molecular weight compound.

[0082] The first component is preferably a compound including at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2).

[0083] When the first component is a compound containing at least one structure selected from the structure represented by formula (1) and the structure represented by the following formula (2), excellent solvent resistance and excellent antireflection performance can be imparted to the resist underlayer film obtained from the resist underlayer film-forming composition.

[0084]

[0085] (In the formula (1), X1 represents a group represented by any one of the following formulae (1-1) to (1-4). Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (1-5).

[0086] In formula (2), Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.

[0087]

[0088] (In formulas (1-1) to (1-3), R1 to R5 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, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms. R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0089] In the formula (1-4), Z3 represents a single bond or a divalent group represented by the following formula (1-5).

[0090] * represents a connecting bond. *1 represents a connecting bond bonded to a carbon atom in formula (1). *2 represents a connecting bond bonded to a nitrogen atom in formula (1).

[0091]

[0092] (In formula (1-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a connecting bond to the nitrogen atom in formula (1) or formula (1-4). *4 represents a connecting bond.)

[0093] <<Formula (1)>>

[0094] Examples of the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom in R1 to R5 of formulae (1-1) to (1-3) include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthioalkyl group having 2 to 10 carbon atoms.

[0095] Furthermore, the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may contain two or more oxygen atoms or sulfur atoms.

[0096] From the viewpoint of suitably obtaining the effects of the present invention, X1 in formula (1) is preferably represented by formula (1-3) or formula (1-4).

[0097] Examples of the formula (1) include the structures shown below.

[0098]

[0099]

[0100]

[0101] In the above structure, * represents a connecting bond.

[0102] <<Formula (2)>>

[0103] Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.

[0104] The aromatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring. The aromatic hydrocarbon ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring.

[0105] The aliphatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring. The aliphatic hydrocarbon ring is not particularly limited, and examples thereof include a cyclohexane ring and the like.

[0106] Q1 is preferably represented by the following formula (2-1).

[0107]

[0108] (In formula (2-1), Q 11 represents a divalent organic group represented by any one of the following formulae (2-1-1) to (2-1-4). n1 and n2 each independently represent 0 or 1. * represents a connecting bond. )

[0109]

[0110] (In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a connecting bond.

[0111] In formula (2-1-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 21 When there are 2 or more R 21 It can be the same or different.

[0112] In formula (2-1-2), Z4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. 22 When there are 2 or more R 22 Can be the same or different. 23 When there are 2 or more R 23 It can be the same or different.

[0113] In formula (2-1-3), n14 represents an integer of 0 to 4. 24 When there are 2 or more R 24 It can be the same or different.

[0114] In formula (2-1-4), Z5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. 25 When there are 2 or more R 25 Can be the same or different. 26 When there are 2 or more R 26 Can be the same or different.)

[0115] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0116] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic chain. Examples of the straight chain or branched chain alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, etc. Examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0117] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, an isopropoxy group, and the like.

[0118] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0119] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.

[0120] In the present specification, examples of the alkynyl group include groups in which the double bond of the alkenyl group exemplified in the above-mentioned "alkenyl group" is replaced with a triple bond.

[0121] In the present specification, examples of the alkenyloxy group include vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, and prenyloxy.

[0122] In the present specification, examples of the alkynyloxy group include a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a 2-methyl-2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

[0123] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0124] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

[0125] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group and the like.

[0126] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0127] In the present specification, examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.

[0128] Examples of the structure represented by formula (2-1) include the following structures.

[0129]

[0130]

[0131] In the above structure, * represents a connecting bond.

[0132] In addition, the first component is preferably a compound including at least one structure selected from the group consisting of a structure represented by the following formula (11) and a structure represented by the following formula (12).

[0133] The first component is preferably a compound containing at least one structure selected from the group consisting of the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (11), and the structure represented by formula (12).

[0134]

[0135] (In formula (11), X1 represents a group represented by any one of the above formulas (1-1) to (1-3) and the following formula (1-4A). Z1 and Z2 each independently represent a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in formula (1-5) represents a connecting bond bonded to the nitrogen atom in formula (11)). A1, A2, A3, A4, A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group. * represents a connecting bond.

[0136] In formula (12), Q 11 represents a divalent organic group represented by any one of the above formulae (2-1-1) to (2-1-4). n1 and n2 each independently represent 0 or 1. A 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a connecting bond. )

[0137]

[0138] (In formula (1-4A), Z3 represents a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in the above formula (1-5) represents a bond bonded to the nitrogen atom in formula (1-4A)). A7, A8 and A9 each independently represent a hydrogen atom, a methyl group or an ethyl group. * represents a bond. *1 represents a bond bonded to a carbon atom in formula (11). *2 represents a bond bonded to a nitrogen atom in formula (11).)

[0139] The first component preferably includes at least one of a structure represented by the following formula (E-1) and a structure represented by the following formula (E-2). If the first component includes these structures, the solubility of the first component in water can be improved.

[0140]

[0141] (In formula (E-1) and formula (E-2), * represents a connecting bond.)

[0142] It is preferred that the first component has a plurality of structures represented by formula (E-1) and (E-2), and it is more preferred that the compound as the first component has 2 to 3 structures represented by formula (E-1) and (E-2).

[0143] The molecular weight of the first component is not particularly limited.

[0144] From the viewpoint of solubility in water, the weight average molecular weight of the first component is preferably smaller.

[0145] The weight average molecular weight of the first component is, for example, 300 to 100,000, preferably 300 to 50,000, more preferably 300 to 10,000, particularly preferably 300 to 5,000.

[0146] An example method for producing the first component will be described.

[0147] An example of the first component can be obtained by, for example, the following reactions (I) to (III).

[0148] (I): Reaction of at least one of a compound represented by the following formula (11A) and a compound represented by the following formula (12A) with a compound represented by the following formula (EA).

[0149]

[0150] (In formula (11A), X1 represents a group represented by any one of the above formulas (1-1) to (1-3) and the following formula (1-4B). Z1 and Z2 each independently represent a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in formula (1-5) represents a connecting bond bonded to the nitrogen atom in formula (11A)). A1, A2, A3, A4, A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group.

[0151] In formula (12A), Q 11 represents a divalent organic group represented by any one of the above formulae (2-1-1) to (2-1-4). n1 and n2 each independently represent 0 or 1. A 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. )

[0152]

[0153] (In formula (1-4B), Z3 represents a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in formula (1-5) represents a bond bonded to the nitrogen atom in formula (1-4B)). A7, A8 and A9 each independently represent a hydrogen atom, a methyl group or an ethyl group. *1 represents a bond bonded to a carbon atom in formula (11A). *2 represents a bond bonded to a nitrogen atom in formula (11A).)

[0154]

[0155] Examples of the compound represented by formula (11A) include the following compounds.

[0156]

[0157]

[0158]

[0159]

[0160] Examples of the compound represented by formula (12A) include the following compounds.

[0161]

[0162]

[0163] (II): Reaction of at least one of a compound represented by the following formula (11B) and a compound represented by the following formula (12A) with a compound represented by the following formula (EB).

[0164]

[0165] (In formula (11B), X1 represents a group represented by any one of the above formulas (1-1) to (1-3) and the following formula (1-4C). Z1 and Z2 each independently represent a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in formula (1-5) represents a connecting bond bonded to the nitrogen atom in formula (11B)).

[0166] In formula (12B), Q 11 represents a divalent organic group represented by any one of the above formulae (2-1-1) to (2-1-4). n1 and n2 each independently represent 0 or 1.

[0167]

[0168] (In formula (1-4C), Z3 represents a single bond or a divalent group represented by the above formula (1-5) (wherein *3 in formula (1-5) represents a bond bonded to the nitrogen atom in formula (1-4C)). *1 represents a bond bonded to the carbon atom in formula (11B). *2 represents a bond bonded to the nitrogen atom in formula (11B).)

[0169]

[0170] Examples of the compound represented by formula (11B) include the following compounds.

[0171]

[0172] Examples of the compound represented by formula (12B) include the following compounds.

[0173]

[0174] (III): Reaction of at least one of the compound represented by the above formula (11A) and the compound represented by the above formula (12A) with a compound represented by the following formula (EC).

[0175]

[0176] (In formula (EC), Q 21 represents a single bond or a divalent organic group. )

[0177] The divalent organic group may be, for example, a divalent organic group having 1 to 20 carbon atoms or a divalent organic group having 1 to 10 carbon atoms.

[0178] The divalent organic group may have a hetero atom. Examples of the hetero atom include an oxygen atom and a sulfur atom.

[0179] Examples of the divalent organic group include hydrocarbon groups having a carbon number of 1 to 10. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0180] Examples of the divalent organic group include hydrocarbon groups having 1 to 10 carbon atoms substituted with a hydroxyl group or a mercapto group. Examples of the hydrocarbon group include aliphatic hydrocarbon groups.

[0181] Examples of the divalent organic group include hydrocarbon groups having 2 to 10 carbon atoms interrupted by oxygen atoms or sulfur atoms. Examples of the hydrocarbon group include aliphatic hydrocarbon groups.

[0182] Examples of the compound represented by formula (EC) include the following compounds.

[0183]

[0184] Reactions (I) to (III) can be carried out in the presence of a catalyst, for example. The catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride. The amount of the catalyst used can be selected from a range of 0.1 to 10% by mass relative to the total mass of the polymer raw material used in the reaction. The temperature and time for the polymerization reaction can be selected from the most suitable conditions within the range of 80 to 160° C. and 2 to 50 hours, for example.

[0185] <Second ingredient>

[0186] The second component is used to improve the coating properties of the resist underlayer film-forming composition.

[0187] The second component is a water-soluble polymer.

[0188] The second component is a compound different from the first component.

[0189] The water-soluble polymer is a polymer compound that dissolves 1 g or more in 100 g of water at 25°C, preferably 5 g or more in 100 g of water at 25°C, and more preferably 10 g or more in 100 g of water at 25°C.

[0190] The water-soluble polymer is not particularly limited, and examples thereof include polyvinyl alcohol, water-soluble cellulose, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinyl pyrrolidone, polyacrylic acid, polystyrene sulfonic acid, and polyvinyl acetamide.

[0191] The so-called polyvinyl alcohol is a polymer obtained by hydrolyzing polyvinyl acetate and converting the acetyl group in the polyvinyl acetate molecule into a hydroxyl group. The value obtained by expressing the proportion of the hydroxyl group in mol% is called the saponification degree. Polyvinyl alcohol is known to have various properties according to its saponification degree. For example, polyvinyl acetate (saponification degree mol 0%) is generally insoluble in water, and polyvinyl alcohol with a saponification degree of 100 mol% is known to be water-soluble. Among polyvinyl alcohols, when the saponification degree is less than 60 mol%, the solubility in water becomes poor, and when the saponification degree is less than 30 mol%, it is substantially completely insoluble. In addition, on the contrary, even if the saponification degree is too high, the solubility becomes low, and polyvinyl alcohol with 85 to 90 mol% has the highest solubility. In the present invention, it is preferred to use polyvinyl alcohol with a saponification degree of 70 mol% or more. Generally, when the saponification degree is higher, the developer resistance becomes better, so it is preferred to use polyvinyl alcohol with a saponification degree of 75 mol% or more. However, if the saponification degree is too high, the storage stability of the composition (generation of insoluble foreign matter) tends to deteriorate. Therefore, the saponification degree of the polyvinyl alcohol is preferably 99 mol % or less, more preferably 98 mol % or less.

[0192] The degree of polymerization of polyvinyl alcohol is usually represented by the viscosity of a 4% by mass aqueous solution (20° C.), which is usually about 1 to 80 cps (mPa·s). Among them, the polyvinyl alcohol used in the present invention preferably has a viscosity of 1 cps or more, and more preferably has a viscosity of 2 cps or more. In addition, the upper limit of the viscosity is preferably 70 cps, and the upper limit of the viscosity is more preferably 65 cps, 50 cps, 40 cps, 30 cps, 20 cps, 10 cps, 8 cps or 5 cps. The range of viscosity is, for example, 1 to 20 cps, 2 to 10 cps, 3 to 8 cps.

[0193] The polyvinyl alcohol may be a polyvinyl alcohol modified by replacing a part of the hydroxyl groups with an alkyl ether group, an alkyloxymethyl group, an acetoacetate group or the like.

[0194] The water-soluble cellulose is not particularly limited, and examples thereof include alkyl celluloses such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; and hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose.

[0195] Among them, hydroxypropyl cellulose is more preferred.

[0196] Regarding hydroxypropyl cellulose, various products with different viscosities are sold on the market by various companies, and all of them can be used in the present invention. The viscosity of a 2 mass % aqueous solution (20° C.) of hydroxypropyl cellulose is not particularly limited and can be appropriately selected according to the purpose, but is preferably 2.0 mPa·s (centipoise, cps) to 4,000 mPa·s (centipoise, cps).

[0197] In addition, it is considered that the viscosity of hydroxypropyl cellulose depends on the weight average molecular weight, substitution degree and molecular weight of hydroxypropyl cellulose.

[0198] The weight average molecular weight of hydroxypropyl cellulose is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 15,000 to 400,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0199] There is no restriction|limiting in particular as a commercial item of hydroxypropyl cellulose, According to the objective, it can select suitably, For example, the following commercial items are mentioned.

[0200] HPC-SSL with a molecular weight of 15,000 to 30,000 and a viscosity of 2.0 mPa·s to 2.9 mPa·s (manufactured by Nippon Soda Co., Ltd.)

[0201] HPC-SL with a molecular weight of 30,000 to 50,000 and a viscosity of 3.0 mPa·s to 5.9 mPa·s (manufactured by Nippon Soda Co., Ltd.)

[0202] HPC-L with a molecular weight of 55,000 to 70,000 and a viscosity of 6.0 mPa·s to 10.0 mPa·s (manufactured by Nippon Soda Co., Ltd.)

[0203] HPC-M with a molecular weight of 110,000 to 150,000 and a viscosity of 150 mPa·s to 400 mPa·s (manufactured by Nippon Soda Co., Ltd.)

[0204] HPC-H with a molecular weight of 250,000 to 400,000 and a viscosity of 1,000 to 4,000 mPa·s (manufactured by Nippon Soda Co., Ltd.)

[0205] Among them, HPC-SSL having a molecular weight of 15,000 to 30,000 and a viscosity of 2.0 mPa·s to 2.9 mPa·s is preferred.

[0206] In addition, in the said commercial product, the molecular weight was measured by gel permeation chromatography (GPC), and the viscosity was measured by 2 mass % aqueous solution (20 degreeC).

[0207] The polystyrene sulfonic acid is not particularly limited as long as it is water-soluble, and its sulfonation rate may be 100% or less than 100%. The sulfonation rate is, for example, 80% to 100%. Here, the so-called "sulfonation rate" refers to the molar ratio (%) of the "styrene unit having a sulfonic acid group" in the total of the "styrene unit having a sulfonic acid group" and the "styrene unit" in the molecule of polystyrene sulfonic acid.

[0208] That is, the polystyrene sulfonic acid may be a homopolymer consisting only of a repeating unit represented by the following formula (SS), or may be a copolymer having a repeating unit represented by the following formula (SS) and a repeating unit represented by the following formula (St).

[0209]

[0210] Examples of the styrenesulfonic acid constituting the polystyrenesulfonic acid include 4-styrenesulfonic acid.

[0211] The content of the second component (water-soluble polymer) in the resist underlayer film-forming composition is not particularly limited.

[0212] By adding a small amount of the second component to the resist underlayer film-forming composition, the coating properties of the resist underlayer film-forming composition can be improved.

[0213] Therefore, the mass ratio of the first component to the second component (first component:second component) in the resist underlayer film-forming composition is preferably 99:1 to 50:50, more preferably 99:1 to 75:25, and particularly preferably 99:1 to 90:10.

[0214] <Crosslinking agent>

[0215] The resist underlayer film-forming composition preferably contains a cross-linking agent.

[0216] The cross-linking agent which may be contained in the resist underlayer film-forming composition as an optional component has, for example, a functional group which reacts by itself.

[0217] Examples of the crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethyl glycoluril) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0218] The crosslinking agent may be a nitrogen-containing compound described in International Publication No. 2017 / 187969 and having 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom in one molecule.

[0219]

[0220] (In formula (1d), R1 represents a methyl group or an ethyl group. * represents a bond to the nitrogen atom.)

[0221] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0222]

[0223] (In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0224] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0225]

[0226] A nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0227]

[0228] (In formula (2d) and formula (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond to the nitrogen atom.)

[0229] The glycoluril derivative represented by the above formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0230] An example of the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) in one molecule is a glycoluril derivative represented by the following formula (2E).

[0231]

[0232] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0233] Examples of the glycoluril derivatives represented by the formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). In addition, examples of the compounds represented by the formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0234]

[0235] Regarding the nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) bonded to a nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0236] The crosslinking agent may be a crosslinking compound represented by the following formula (G-1) or formula (G-2) described in International Publication No. 2014 / 208542.

[0237]

[0238] (Where Q 1 represents a single bond or m1-valent organic group, R 1 and R 4 Each represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 Each represents a hydrogen atom or a methyl group, R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

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

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

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

[0242] The crosslinking compound represented by the above formula (G-1) or (G-2) may be a compound obtained by reacting a compound represented by the following formula (G-3) or (G-4) with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0243]

[0244] (Where Q 2 Represents a single bond or an m2-valent organic group. 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0245] n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and 3≤(n9+n10+n11+n12)≤6.

[0246] n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and 2≤(n13+n14+n15+n16)≤5.

[0247] m2 represents an integer from 2 to 10. )

[0248] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0249]

[0250]

[0251]

[0252]

[0253]

[0254] Examples of the compounds represented by formula (G-3) and formula (G-4) include the following.

[0255]

[0256]

[0257] In the formula, Me represents a methyl group.

[0258] The entire disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0259] When the crosslinking agent is used, the content ratio of the crosslinking agent in the resist underlayer film-forming composition is, for example, 1 to 50 mass %, or preferably 5 to 40 mass % based on the total of the first component and the second component.

[0260] When the crosslinking agent is used, the content ratio of the crosslinking agent in the resist underlayer film forming composition is, for example, 1 mass % to 50 mass %, or preferably 5 mass % to 40 mass % based on the total amount of the first component.

[0261] <Curing Catalyst>

[0262] As the curing catalyst which may be contained in the resist underlayer film-forming composition as an optional component, any of a thermal acid generator and a photoacid generator may be used, but a thermal acid generator is preferably used.

[0263] 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-toluenesulfonate), pyridinium phenolsulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium p-phenolsulfonate), pyridinium trifluoromethanesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0264] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0265] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0266] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0267] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0268] The curing catalyst may be used alone or in combination of two or more.

[0269] When a curing catalyst is used, the content ratio of the curing catalyst relative to the cross-linking agent is, for example, 0.1 mass % to 50 mass %, or preferably 1 mass % to 30 mass %.

[0270] <Solvent>

[0271] The resist underlayer film-forming composition contains a solvent.

[0272] The solvent includes water.

[0273] The solvent may contain an organic solvent in addition to water.

[0274] The solvent preferably contains 50% by mass or more of water relative to the solvent, more preferably contains 70% by mass or more of water relative to the solvent, further preferably contains 80% by mass or more of water relative to the solvent, and particularly preferably contains 90% by mass or more of water relative to the solvent.

[0275] As the organic solvent, an organic solvent generally used in a chemical solution for semiconductor photolithography process is preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate , ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0276] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0277] <Other ingredients>

[0278] A surfactant may be further added to the resist underlayer film-forming composition in order to prevent the generation of pinholes, streaks, and the like and to further improve coating properties on surface unevenness.

[0279] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Non-ionic surfactants such as anhydride tristearate and other polyoxyethylene sorbitan fatty acid esters, Etotron EF301, EF303, EF352 (Todo Co., Ltd. Manufactured by プロダクツ, trade name), メガファック F171, F173, R-30 (made by DIC Co., Ltd., trade name), フロラード FC430, FC431 (trade name, manufactured by Sumitomo Slide Group Co., Ltd.), ASHIGADO AG710, S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade name, manufactured by Asahi Glass Co., Ltd.), and other fluorine-based surfactants, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0280] The amount of these surfactants blended is not particularly limited, but is usually 2.0 mass % or less, preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition.

[0281] These surfactants may be added alone or in combination of two or more.

[0282] The film constituting components contained in the resist underlayer film-forming composition, that is, the components other than the solvent, are contained in an amount of, for example, 0.01% by mass to 10% by mass of the resist underlayer film-forming composition.

[0283] The resist underlayer film-forming composition of the present invention can be manufactured, for example, by mixing the first component and a solvent, etc., using a known method. In order to use it as a resist underlayer film-forming composition, it must be in a uniform solution state. The manufactured composition is preferably filtered using a filter, etc., to remove metal impurities, foreign matter, etc. present in the composition.

[0284] One of the criteria for evaluating whether the resist underlayer film forming composition is in a uniform solution state is to observe the permeability through a specific microporous filter. The resist underlayer film forming composition involved in the present invention preferably passes through a microporous filter with a pore size of 0.1μm, 0.05μm, 0.03μm, 0.02μm, and 0.01μm to be in a uniform solution state.

[0285] As the material of the above-mentioned microporous filter, fluororesins such as PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon can be cited, but PTFE (polytetrafluoroethylene) is preferred. The resist underlayer film-forming composition contains water as a solvent, and therefore, the filter used in filtering the resist underlayer film-forming composition is preferably a filter that has been subjected to a hydrophilic treatment.

[0286] (Resist Underlayer Film)

[0287] The resist underlayer film of the present invention is a cured product of the above-mentioned resist underlayer film-forming composition.

[0288] The resist underlayer film can be produced, for example, by applying the resist underlayer film-forming composition described above onto a semiconductor substrate and firing the resulting composition.

[0289] Examples of the semiconductor substrate to which the resist underlayer film-forming composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0290] In the case of using a semiconductor substrate having an inorganic film formed on the surface, the inorganic film can be formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). As the above-mentioned inorganic film, for example, polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass, borophosphorus silicon glass) film, titanium nitride film, titanium oxynitride film, tungsten film, gallium nitride film and gallium arsenide film can be cited. The inorganic film can be a single layer or a multilayer with more than two layers. In the case of more than one layer, each layer can be the same type of inorganic film or different types of inorganic films.

[0291] The thickness of the inorganic film is not particularly limited.

[0292] On such a semiconductor substrate, the resist lower film forming composition of the present invention is applied by a suitable coating method such as a spinner or a coater. Then, a heating means such as a hot plate is used to bake, thereby forming a resist lower film. As baking conditions, it can be appropriately selected 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.

[0293] The thickness of the resist underlayer film is, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (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 (500 nm), and 0.006 μm (5 nm) to 0.05 μm (500 nm). 0nm), 0.003μm (3nm) ~ 0.03μm (30nm), 0.003μm (3nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.003μm (3nm) ~ 0.01μm (10nm), 0.005μm (5nm) ~ 0.01μm (10nm), 0.003μm (3nm) ~ 0.006μm (6nm), or 0.005μm (5nm).

[0294] The method for measuring the film thickness of the resist underlayer film in this specification is as follows.

[0295] ·Measurement device name: Optical interference film thickness meter (Product name: Nanotron 6100, manufactured by Nanotron Co., Ltd.)

[0296] Arithmetic average of 4 points (for example, 4 points are measured at 1 cm intervals in the X direction of the wafer)

[0297] (Substrates for semiconductor processing)

[0298] The semiconductor processing substrate of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.

[0299] As the semiconductor substrate, for example, the above-mentioned semiconductor substrates can be mentioned.

[0300] The resist underlayer film is disposed on, for example, a semiconductor substrate.

[0301] (Semiconductor device manufacturing method, pattern forming method)

[0302] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0303] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention; and

[0304] ・Step of forming a resist film on the resist underlayer film

[0305] The pattern forming method of the present invention includes at least the following steps.

[0306] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention;

[0307] A step of forming a resist film on the resist underlayer film;

[0308] A step of irradiating the resist film with light or electron beams and then developing the resist film to obtain a resist pattern; and

[0309] ・The process of etching the resist underlayer film using the resist pattern as a mask

[0310] Usually, a resist film is formed on the resist underlayer film.

[0311] The thickness of the resist film is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 80 nm or less. In addition, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.

[0312] The resist film formed on the resist underlayer film by a known method (e.g., coating and firing) is not particularly limited as long as it is a resist film that responds to light or electron beam (EB) for irradiation. Any of negative photoresists and positive photoresists can be used.

[0313] The light or electron beam is not particularly limited, and examples thereof include i-ray (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet; 13.5 nm), and EB (electron beam).

[0314] It should be noted that, in this specification, a resist that responds to EB is also referred to as a photoresist.

[0315] As photoresists, there are the following photoresists: positive photoresists composed of novolac resin and 1,2-diazonaphthoquinone sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes under the action of an acid to increase the alkali dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low molecular compound that decomposes under the action of an acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; and chemically amplified photoresists composed of a binder having a group that decomposes under the action of an acid to increase the alkali dissolution rate, a low molecular compound that decomposes under the action of an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; resists containing metal elements, etc. For example, JSR Corp.'s product name V146G, Shipley's product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430, etc. In addition, for example, fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be mentioned.

[0316] In addition, 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, Japanese Patent Application 2018-180525, WO2018 / 190088, Japan Patent Application 2018-070596, Japan Patent Application 2018-028090, Japan Patent Application 2016-153409, Japan Patent Application Open 2016-130240, Japan Special Open 2016-108325, Japan Special Open 2016-047920, Japan Special Open 2016-035570, Japan Special Opening 2016-035567, Japanese Special Opening 2016-035565, Japanese Special Opening 2019-101417, Japanese Special Opening 2019-11737 3. Japan Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019- 061217, Japanese Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 2 011-043749, Japanese Patent Application Laid-Open No. 2010-181857, Japanese Patent Application Laid-Open No. 2010-128369, WO2018 / 031896, Japanese Patent Application Laid-Open No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Laid-Open No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Laid-Open No. 2016-29498, Japanese Patent Application Laid-Open No. 2011-253185, etc., so-called resist compositions, and metal-containing resist compositions, but not limited thereto.

[0317] Examples of the resist composition include the following compositions.

[0318] An active light-sensitive or radiation-sensitive resin composition comprises a resin A containing a repeating unit having an acid-decomposable group, wherein a polar group is protected by a protecting group that is released by an acid, and a compound represented by the following general formula (21).

[0319] In the general formula (21), m represents an integer of 1-6.

[0320] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0321] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0322] L2 represents an alkylene group which may have a substituent or a single bond.

[0323] W1 represents a cyclic organic group which may have a substituent.

[0324] M + Represents a cation.

[0325] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography contains a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the third to seventh periods of the third to fifteenth groups of the periodic table.

[0326] A radiation-sensitive resin composition comprising: a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) and containing an acid-dissociable group; and an acid generator.

[0327]

[0328] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. R 1 is a hydroxyl group, a sulfanyl group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, a plurality of R 1 Same or different. 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 3 is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid dissociable group. Z is a single bond, an oxygen atom or a sulfur atom. 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. )

[0329] A resist composition comprising: a resin (A1) comprising a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid-labile group; and an acid generator.

[0330]

[0331] [Wherein,

[0332] R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom, and X 1 Represents a single bond, -CO-O-* or -CO-NR 4 -*, * represents the bond with -Ar, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from a hydroxyl group and a carboxyl group.]

[0333] As the resist film, for example, the following resist films can be mentioned.

[0334] A resist film includes a base resin including a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain by exposure.

[0335]

[0336] (In formula (a1) and formula (a2), R A Each is independently a hydrogen atom or a methyl group. 1 and R 2 Each R is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each independently represents a fluorine atom or a methyl group. m represents an integer from 0 to 4. 1 X is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms and including at least one selected from an ester bond, a lactone ring, a phenylene group and a naphthylene group. 2 is a single bond, an ester bond, or an amide bond. )

[0337] Examples of the resist material include the following resist materials.

[0338] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2).

[0339]

[0340] (In formula (b1) and formula (b2), R A X is a hydrogen atom or a methyl group. 1 is a single bond or an ester group.2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a part of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring, and X 2 At least one hydrogen atom contained in is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf 4 Each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 Can combine to form a carbonyl group. 1 ~R 5 Each is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and a part or all of the hydrogen atoms in these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfonium group, or a group containing a sulfonium salt, and a part of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate group. In addition, R 1 With R 2 They may bond to form a ring together with the sulfur atom to which they are bonded.)

[0341] A resist material includes a base resin including a polymer containing a repeating unit represented by the following formula (a).

[0342]

[0343] (In formula (a), R A is a hydrogen atom or a methyl group. 1 is a hydrogen atom or an acid-labile group. 2 X is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 X is a single bond, a phenylene group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms which may contain a lactone ring. 2 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. Wherein, m+u is an integer of 1 to 4.)

[0344] A resist composition which generates an acid upon exposure and whose solubility in a developer changes under the action of the acid.

[0345] The resist composition contains a base material component (A) whose solubility in a developer changes under the action of an acid and a fluorine additive component (F) which shows decomposability with respect to an alkali developer.

[0346] The above-mentioned fluorine additive component (F) contains a fluororesin component (F1) having a structural unit (f1) containing an alkali-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0347]

[0348] [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.]

[0349] The above-mentioned structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0350]

[0351] [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 haloalkyl group having 1 to 5 carbon atoms. X is a divalent linking group not having an 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.]

[0352] Examples of the coating, coating solution and coating composition include the following.

[0353] A coating which contains a metal oxo-hydroxo network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0354] An inorganic oxo / hydroxy-based composition.

[0355] A coating solution which contains: 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 (wherein, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R’ n SnX4-n (wherein, n = 1 or 2), or a mixture thereof, wherein R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; the hydrolyzable metal compound is represented by the formula MX' v (wherein, M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0356] A coating solution, which is a coating solution containing an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (wherein, 0 < x < 3), and contains about 0.0025 M to about 1.5 M of tin in the above solution, R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, and the above alkyl group or cycloalkyl group is bonded to tin at a secondary carbon atom or a tertiary carbon atom).

[0357] An aqueous inorganic pattern forming precursor solution, which is a mixture containing water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand (which contains a peroxide group).

[0358] Irradiation with light or electron beams is carried out through, for example, a mask (intermediate mask) for forming a specified pattern.

[0359] There is no particular limitation on the exposure amount and the irradiation energy of the electron beams.

[0360] After irradiation with light or electron beams and before development, baking (PEB: Post Exposure Bake) can be carried out.

[0361] There is no particular limitation on the baking temperature, but it is preferably 60 °C to 150 °C, more preferably 70 °C to 120 °C, and particularly preferably 75 °C to 110 °C.

[0362] There is no particular limitation on the baking time, but it is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0363] In development, an alkali developer can be used, for example.

[0364] Examples of the development temperature include 5 °C to 50 °C.

[0365] Examples of the development time include 10 seconds to 300 seconds.

[0366] As an alkali developer, for example, an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, an alcohol amine such as dimethylethanolamine, triethanolamine, a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, a cyclic amine such as pyrrole, piperidine, etc. can be used. Furthermore, an appropriate amount of alcohols such as isopropanol, a nonionic surfactant, etc. can also be added to the aqueous solution of the above-mentioned alkalis for use. Among them, a preferred developer is an aqueous solution of a quaternary ammonium salt, and an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline are further preferred. Furthermore, a surfactant, etc. can also be added to these developers. The following method can also be adopted: instead of an alkali developer, an organic solvent such as butyl acetate is used for development to develop the portion where the alkali dissolution rate of the photoresist is not increased.

[0367] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred.

[0368] When the inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate is processed by a known method (dry etching method, etc.), thereby manufacturing a semiconductor device.

[0369] Example

[0370] Next, the present invention will be specifically described with reference to synthesis examples and working examples, but the present invention is not limited thereto.

[0371] The weight average molecular weights of the polymers shown in Synthesis Examples 1 to 10 below are the results of measurements obtained by gel permeation chromatography (hereinafter referred to as GPC). In the measurement, a GPC apparatus manufactured by Tosoh Corporation was used, and the measurement conditions and the like were as follows.

[0372] Column temperature: 40°C

[0373] Flow rate: 0.35ml / min

[0374] Eluent: Tetrahydrofuran (THF)

[0375] Standard sample: Polystyrene (Tosoh Corporation)

[0376] <Synthesis example 1>

[0377] A reaction flask to which 24.52 g of propylene glycol monomethyl ether was added to 16.00 g of MeDGIC (manufactured by Shikoku Chemical Industry Co., Ltd., 28.8% by mass propylene glycol monomethyl ether solution), 3.88 g of 1-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.45 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 18 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-1), and the weight average molecular weight Mw measured by GPC and converted to polystyrene is 330. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0378]

[0379] <Synthesis example 2>

[0380] A reaction flask to which 42.68 g of propylene glycol monomethyl ether was added to 5.00 g of TEPIC (manufactured by Nissan Chemical Co., Ltd.), 5.45 g of 1-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.21 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 23 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-2), and the weight average molecular weight Mw measured by GPC and converted to polystyrene is 470. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0381]

[0382] <Synthesis example 3>

[0383] A reaction flask to which 20.32 g of propylene glycol monomethyl ether was added to 2.50 g of EX-201 (manufactured by Nagasechem Tech Co., Ltd.), 2.31 g of 1-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.26 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 18 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-3), and the weight average molecular weight Mw measured by GPC and converted to polystyrene is 500. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0384]

[0385] <Synthesis example 4>

[0386] A reaction flask to which 37.10 g of propylene glycol monomethyl ether was added to 5.00 g of HP-4032D (manufactured by DIC Corporation), 3.96 g of 1-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 18 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-4), and the weight average molecular weight Mw measured by GPC and converted to polystyrene is 700. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0387]

[0388] <Synthesis example 5>

[0389] A reaction flask to which 20.36 g of propylene glycol monomethyl ether was added to 2.30 g of TEPIC (manufactured by Nissan Chemical Co., Ltd.), 2.74 g of succinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.04 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred at 90° C. for 21 hours under a nitrogen atmosphere. The obtained reaction product corresponds to the following formula (X-5), and the weight average molecular weight Mw measured by GPC and in terms of polystyrene conversion is 800. Then, the solution of the reaction product was added dropwise to a hexane solution, and the obtained precipitate was separated by filtration and dried under vacuum at 40° C.

[0390] The obtained compound was dissolved in ultrapure water so as to become 10 mass %.

[0391]

[0392] <Synthesis example 6>

[0393] A reaction flask to which 17.47 g of propylene glycol monomethyl ether was added to 2.20 g of MAICA (made by Shikoku Chemical Industry Co., Ltd.), 2.00 g of glycidol (made by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.16 g of tetrabutylphosphonium bromide (made by Hokuko Chemical Co., Ltd.) was heated and stirred for 22 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-6), and the weight average molecular weight Mw measured by GPC and converted to polystyrene is 400. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0394]

[0395] <Synthesis Example 7>

[0396] A reaction flask to which propylene glycol monomethyl ether 21.73 g was added to 3.37 g of monomethyl dicarboxymethyl isocyanuric acid, 2.00 g of glycidol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 22 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to the following formula (X-7), and the weight average molecular weight Mw measured by GPC and polystyrene conversion is 460. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under vacuum at 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of 10% by mass.

[0397]

[0398] <Synthesis example 8>

[0399] A reaction flask to which 21.56 g of propylene glycol monomethyl ether was added to 2.90 g of tricarboxymethyl isocyanuric acid, 2.40 g of glycidol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.08 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) was heated and stirred for 21 hours at 105° C. under a nitrogen atmosphere. The obtained reaction product corresponds to the following formula (X-8), and the weight average molecular weight Mw measured by GPC and in terms of polystyrene conversion is 550. Then, the solution of the reaction product was added dropwise to a hexane solution, and the obtained precipitate was separated by filtration and dried under vacuum at 40° C.

[0400] The obtained compound was dissolved in ultrapure water so as to become 10 mass %.

[0401]

[0402] <Synthesis Example 9>

[0403] A reaction flask to which 17.54 g of propylene glycol monomethyl ether was added to 2.16 g of isophthalic acid (Tokyo Chemical Industry Co., Ltd.), 2.00 g of glycidol (Fuji Film Wako Pure Chemical Industries, Ltd.), and 0.22 g of tetrabutylphosphonium bromide (Hokuko Chemical Co., Ltd.) was heated and stirred for 22 hours at 105 ° C under a nitrogen atmosphere. The obtained reaction product is equivalent to formula (x-9), and the weight average molecular weight Mw measured by using GPC and converted to polystyrene is 450. Then, the solution of the reaction product is added dropwise to a hexane solution, and the obtained precipitate is separated by filtration and dried under the condition of vacuum 40 ° C. The obtained compound is dissolved in ultrapure water in a manner of becoming 10% by mass.

[0404]

[0405] <Synthesis example 10>

[0406] A reaction flask containing 25.7 g of ultrapure water was added to 3.00 g of TEPIC (manufactured by Nissan Chemical Co., Ltd.), 3.29 g of 1-thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.13 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) and heated and stirred at 100° C. for 14 hours under a nitrogen atmosphere. The obtained reaction product corresponds to the following formula (X-2), and the weight average molecular weight Mw measured by GPC and in terms of polystyrene conversion is 530.

[0407]

[0408] <Example 1>

[0409] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 1 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0410] <Example 2>

[0411] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0412] <Example 3>

[0413] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 3 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0414] <Example 4>

[0415] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 4 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0416] <Example 5>

[0417] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 5 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0418] <Example 6>

[0419] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 6 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0420] <Example 7>

[0421] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 7 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0422] <Example 8>

[0423] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 8 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0424] <Example 9>

[0425] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 9 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0426] <Example 10>

[0427] 0.18 g of tetramethoxymethyl glycoluril, 0.02 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of polyvinyl alcohol (PXP-05, Nippon Acid Bio-Poval Co., Ltd.), and 92.41 g of ultrapure water were added to 7.33 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0428] <Example 11>

[0429] 0.03 g of pyridinium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.), and 90.72 g of ultrapure water were added to 9.19 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0430] <Example 12>

[0431] 0.04 g of polystyrene sulfonic acid (manufactured by Sigmar Dolic) and 86.36 g of ultrapure water were added to 13.59 g of an aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2 to prepare a solution. The solution was filtered using a hydrophilized PTFE syringe filter having a pore size of 0.02 μm to prepare a resist underlayer film-forming composition.

[0432] [Resist solvent resistance test]

[0433] The compositions for forming the resist underlayer film prepared in Examples 1 to 12 were respectively applied (spin-coated) on silicon wafers using a spin coater. On a hot plate, the coated silicon wafer was heated at 205°C for 1 minute to form a film (underlayer film) with a thickness of 25 nm. Next, in order to confirm the solvent resistance of the underlayer film, the silicon wafer after the underlayer film was formed was immersed in a mixed solvent obtained by mixing propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a mass ratio of 7:3 for 1 minute, and after spin drying, it was baked at 100°C for 30 seconds. The film thickness of the protective film before and after immersion in the mixed solvent was measured using an optical interference film thickness meter (product name: Nanos Spice 6100, manufactured by Nanometris Diapan Co., Ltd.).

[0434] In the evaluation of solvent resistance, the film thickness reduction rate (%) of the lower layer film removed by solvent immersion was calculated from the following calculation formula and evaluated.

[0435] Film thickness reduction rate (%) = ((AB) ÷ A) × 100

[0436] A: Film thickness before solvent immersion

[0437] B: Film thickness after solvent immersion

[0438] The results are shown in Table 1. In addition, when the film thickness reduction rate is about 1% or less, it can be said that sufficient solvent resistance is present.

[0439] Table 1

[0440] Example Film thickness reduction rate Example 1 -0.2％ Example 2 0.0％ Example 3 -0.2％ Example 4 0.0％ Example 5 0.0％ Example 6 -0.1％ Example 7 0.0％ Example 8 0.0％ Example 9 -0.2％ Example 10 0.0％ Embodiment 11 -0.1％ Example 12 0.0％

[0441] According to the above results, the film thickness change of the film formed by the resist underlayer film forming composition of Examples 1 to 12 was very small even after being immersed in a solvent. Therefore, the film formed by the resist underlayer film forming composition of Examples 1 to 12 had sufficient solvent resistance to function as an underlayer film.

[0442] It should be noted that in Examples 1, 3, 6, 9, and 11, although the film thickness reduction rate was negative, there was no particular problem.

[0443] [Evaluation of optical parameters]

[0444] The resist underlayer film-forming compositions prepared in Examples 2, 10, 11 and 12 were applied to silicon wafers using a spin coater. The coated silicon wafers were heated at 205° C. for 1 minute on a hot plate to form resist underlayer films (film thickness of 30 nm). Then, for these resist underlayer films, the n value (refractive index) and k value (attenuation coefficient or absorption coefficient) at a wavelength of 193 nm were measured using an ellipsometer (product name: VUV-VASE VU-302, manufactured by JA Woollam). The results of the optical parameter measurements are shown in Table 2.

[0445] Table 2

[0446] Example n / k@193nm Example 2 1.91 / 0.22 Example 10 1.89 / 0.22 Embodiment 11 1.89 / 0.23 Example 12 1.87 / 0.25

[0447] [Formation of resist pattern 1

[0448] The following shows an example of forming a resist underlayer film and forming a resist pattern thereon. Using a spin coater, the resist underlayer film-forming composition prepared in Example 2 is applied to a substrate on which a SiON film (silicon oxide film containing nitrogen) is formed with a thickness of 50 nm on a silicon wafer. Thereafter, baking is performed on a hot plate (205°C, 1 minute) to form a resist underlayer film with a film thickness of 20nm to 30nm. On the resist underlayer film, a commercially available photoresist solution (manufactured by JSR (Co., Ltd., trade name: AR2772) is applied using a spin coater, and baked on a hot plate (e.g., 110°C, 90 seconds) to form a photoresist film with a film thickness of 100nm.

[0449] Next, using a scanner [NSRS307E (wavelength 193nm, NA: 0.85, σ: 0.85 / 0.93 (Dipole) manufactured by (Co., Ltd.) NIKON], after development, exposure was performed through a photomask, and the photomask was set so that the line width of the photoresist and the width between the lines of the photoresist were 0.065μm, that is, 0.065μmL / S (dense line) and 9 such lines were formed. Then, on a hot plate, post-exposure heating (PEB) was performed at 110°C for 90 seconds, and after cooling, development was performed using an industrial standard 60-second single-blade paddle process using a 0.26N tetramethylammonium hydroxide aqueous solution as a developer. Through the above process, a resist pattern was formed.

[0450] The obtained photoresist pattern was observed by scanning electron microscope (SEM) in a cross section perpendicular to the substrate, i.e., the silicon wafer. As a result, it was observed that the cross-sectional shape of the obtained photoresist pattern had a good straight folded edge shape and was roughly rectangular. The SEM image obtained by photographing the cross section of the photoresist pattern finally formed on the substrate using the resist underlayer film forming composition of Example 2 is shown in FIG. Figure 1 .

Claims

1. A resist underlayer film-forming composition comprising a first component, a second component and a solvent, The second component is a water-soluble polymer, The mass ratio of the first component to the second component, i.e., the first component: the second component, is 99:1 to 50:

50. The solvent contains 50% by mass or more of water based on the solvent.

2. A resist underlayer film-forming composition comprising a first component and a solvent, The first component is a compound including at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2), The solvent contains 50% by mass or more of water relative to the solvent, In formula (1), X1 represents a group represented by any one of the following formulae (1-1) to (1-4); Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (1-5); In formula (2), Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; In formulae (1-1) to (1-3), R1 to R5 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, wherein the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms; R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms; R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms; In formula (1-4), Z3 represents a single bond or a divalent group represented by the following formula (1-5); * represents a connecting bond; *1 represents a connecting bond bonded to a carbon atom in formula (1); *2 represents a connecting bond bonded to a nitrogen atom in formula (1); In formula (1-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2; wherein, When m3 is 1, m1 and m2 are not simultaneously 0; *3 represents a connecting bond to the nitrogen atom in formula (1) or formula (1-4); and *4 represents a connecting bond.

3. The resist underlayer film-forming composition according to claim 1, wherein the first component is a compound containing at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2), In formula (1), X1 represents a group represented by any one of the following formulae (1-1) to (1-4); Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (1-5); In formula (2), Q1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; In formulae (1-1) to (1-3), R1 to R5 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, wherein the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms; R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms; R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms; In formula (1-4), Z3 represents a single bond or a divalent group represented by the following formula (1-5); * represents a connecting bond; *1 represents a connecting bond bonded to a carbon atom in formula (1); *2 represents a connecting bond bonded to a nitrogen atom in formula (1); In formula (1-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2; wherein, When m3 is 1, m1 and m2 are not simultaneously 0; *3 represents a connecting bond to the nitrogen atom in formula (1) or formula (1-4); and *4 represents a connecting bond.

4. The resist underlayer film forming composition according to claim 2 or 3, wherein Q1 is represented by the following formula (2-1): In formula (2-1), Q 11 represents a divalent organic group represented by any one of the following formulae (2-1-1) to (2-1-4); n1 and n2 each independently represent 0 or 1; * represents a connecting bond; In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms; * represents a connecting bond; In formula (2-1-1), n3 represents 0 or 1; when n3 is 0, n11 represents an integer from 0 to 4; when n3 is 1, n11 represents an integer from 0 to 6; 21 When there are 2 or more R 21 It can be the same or different; In formula (2-1-2), Z4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms; n12 and n13 each independently represent an integer of 0 to 4; 22 When there are 2 or more R 22 Can be the same or different; in R 23 When there are 2 or more R 23 It can be the same or different; In formula (2-1-3), n14 represents an integer from 0 to 4; 24 When there are 2 or more R 24 It can be the same or different; In formula (2-1-4), Z5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms; n15 and n16 each independently represent an integer of 0 to 4; 25 When there are 2 or more R 25 Can be the same or different; in R 26 When there are 2 or more R 26 It can be the same or different.

5. The resist underlayer film forming composition according to claim 1 or 2, wherein the first component comprises at least one structure represented by the following formula (E-1) and the following formula (E-2), In formula (E-1) and formula (E-2), * represents a connecting bond. 6 . The resist underlayer film-forming composition according to claim 2 , comprising a second component, wherein the second component is a water-soluble polymer. 7 . The resist underlayer film-forming composition according to claim 1 , wherein the water-soluble polymer is at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid, and water-soluble cellulose. 8 . The aqueous composition for forming a resist underlayer film according to claim 6 , wherein a mass ratio of the first component to the second component, i.e., first component:second component, is 99:1 to 50:

50. 9 . The resist underlayer film forming composition according to claim 1 , further comprising a crosslinking agent. 10 . The resist underlayer film forming composition according to claim 1 , further comprising a curing catalyst. 11 . A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to claim 1 or 2.

12. A semiconductor processing substrate comprising: semiconductor substrate, and The resist underlayer film according to claim 11.

13. A method for manufacturing a semiconductor element, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to claim 1 or 2; and A step of forming a resist film on the resist underlayer film.

14. A pattern forming method comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to claim 1 or 2; forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and A step of etching the resist underlayer film using the resist pattern as a mask.

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