Resist underlayer film-forming composition

Abstract

Provided is a resist underlayer film-forming composition that contains: a polymer (A) having a partial structure represented by formula (A); a polymer (B) having a polymerizable multiple bond; and a solvent (C). In formula (A), R11 denotes an (n+2)-valent group having an aromatic hydrocarbon ring and / or an aliphatic hydrocarbon ring. R12 denotes a hydrogen atom or an optionally substituted alkyl group having 1-13 carbon atoms. n is 1 or 2. If n is 2, the two R12 moieties may be the same as, or different from, each other. ＊ denotes a bond.

Description

Composition for forming resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for producing a semiconductor element, and a method for forming a pattern.

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, the integration density of semiconductor devices has increased, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to influences from the semiconductor substrate, etc., has become a major problem. To address this issue, methods of providing a resist underlayer film between the resist and the semiconductor substrate have been widely investigated.

[0003] A resist underlayer film-forming composition has been proposed, which comprises a reaction product of a compound (A) represented by formula (1) (in formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocycle) dissolved in a solvent, a compound (B) having two functional groups reactive with an epoxy group, and a compound (C) having one functional group reactive with an epoxy group (see Patent Document 1).

[0004] International Publication No. 2022 / 075339

[0005] Properties required for a resist underlayer film include, for example, not intermixing with a resist film formed on top (being insoluble in a resist solvent), improving the adhesion of the resist pattern to enable the formation of a fine resist pattern, etc. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film that is capable of forming a fine resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor device, and a pattern formation method that use the composition for forming a resist underlayer film.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0007] That is, the present invention includes the following aspects: [1] A composition for forming a resist underlayer film, comprising: a polymer (A) having a partial structure represented by the following formula (A), a polymer (B) having a polymerizable multiple bond, and a solvent (C): (In formula (A), R １１ represents an (n+2)-valent group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. １２ represents a hydrogen atom, or an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, two R １２ may be the same or different. * represents a bond.) [2] The composition for forming a resist underlayer film according to [1], wherein the polymer (B) is a polymer (B-1) having a structural unit represented by the following formula (B-1) or a polymer (B-2) having a structural unit represented by the following formula (B-2): (In formula (B-1), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.１ represents a single bond or a linking group. ２ represents the monovalent group having a polymerizable multiple bond. (In formula (B-2), 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; Q ２１ represents a divalent organic group. ２１ represents a divalent group having a polymerizable multiple bond.) [3] L in the structural unit represented by formula (B-1) １ -L ２ has a structure represented by the following formula (1a), (1b), or (1c): (In formulas (1a) to (1c), R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. *a and *b represent bonds, with *a being on the main chain side of the polymer (B-1) and *b being on the terminal side of the side chain of the polymer (B-1).) [4] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein the polymer (A) has a structural unit represented by the following formula (A-11): (In formula (A-11), A １ , A ２ , A ３ , A ４ , A ５ and A ６ R each independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ represents an (n+2)-valent organic group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. １２represents a hydrogen atom, or an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, two R １２ may be the same or different.) [5] The composition for forming a resist underlayer film according to [4], wherein Q in formula (A-11) is represented by either formula (A-21) or formula (A-22) below: (In formula (A-21), X １ represents a divalent group represented by the following formula (A-21-1), (A-21-2) or (A-21-3). １ and Z ２ Each of Q independently represents a single bond or a divalent group represented by the following formula (A-21-4). * represents a bond. １ represents a divalent group having an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * represents a bond. (In formulas (A-21-1) to (A-21-3), R １ ~R ５ R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted 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. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ and R ４may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom. (In formula (A-21-4), m1 is an integer of 1 to 4, and m2 is 0 or 1. *3 represents a bond bonded to a nitrogen atom. *4 represents a bond bonded to a carbon atom.) [6] Q in formula (A-22) １ is represented by any one of the following formulas (A-22-1) to (A-22-4): (In formulas (A-22-1) to (A-22-4), R ３１ ~R ３６ each independently represents a halogen atom, a hydroxy 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 bond. In formula (A-22-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer of 0 to 4. When n3 is 1, n11 represents an integer of 0 to 6. R ３１ When is 2 or more, R is 2 or more ３１ In formula (A-22-2), Z may be the same or different. １ 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. R ３２ When is 2 or more, R is 2 or more ３２ may be the same or different. ３３ When is 2 or more, R is 2 or more ３３ In formula (A-22-3), Y may be the same or different. １ and Y ２ each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. R ３４When is 2 or more, R is 2 or more ３４ In formula (A-22-4), Z may be the same or different. ２ 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. R ３５ When is 2 or more, R is 2 or more ３５ may be the same or different. ３６ When is 2 or more, R is 2 or more ３６may be the same or different.) [7] The composition for forming a resist underlayer film according to any one of [1] to [6], wherein the mass ratio of the polymer (A) to the polymer (B) (polymer (A):polymer (B)) is 20:80 to 80:20. [8] The composition for forming a resist underlayer film according to any one of [1] to [7], wherein the solvent (C) contains at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers. [9] The composition for forming a resist underlayer film according to any one of [1] to [8], further containing a crosslinking agent (D).

[10] The composition for forming a resist underlayer film according to [9], wherein the crosslinking agent (D) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[11] The composition for forming a resist underlayer film according to any one of [1] to

[10] , further containing a curing catalyst (E).

[12] The composition for forming a resist underlayer film according to any one of [1] to

[11] , which is used in EUV lithography.

[13] The composition for forming a resist underlayer film according to any one of [1] to

[12] , which is used in forming an underlayer film of a metal-containing resist.

[14] A resist underlayer film that is a cured product of the composition for forming a resist underlayer film according to any one of [1] to

[13] .

[15] A laminate comprising: a semiconductor substrate; and the resist underlayer film according to

[14] .

[16] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[13] ; and forming a resist film on the resist underlayer film.

[17] A pattern forming method comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[13] ; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a composition for forming a resist underlayer film that is capable of forming a fine resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor element, and a pattern forming method, all of which use the composition for forming a resist underlayer film.

[0009] (Composition for forming a resist underlayer film) The composition for forming a resist underlayer film of the present invention contains a polymer (A), a polymer (B), and a solvent (C). The composition for forming a resist underlayer film may also contain a crosslinking agent (D), a curing catalyst (E), and the like. The polymer (A) has a partial structure represented by the following formula (A). The polymer (B) has a polymerizable multiple bond.

[0010] By containing polymer (A) and polymer (B), the composition for forming a resist underlayer film can form a fine resist pattern on the resist underlayer film formed from the composition for forming a resist underlayer film. Although the reason for this is unclear, the present inventors believe that the partial structure represented by formula (A) in polymer (A) and the polymerizable multiple bond in polymer (B) improve the adhesion of the resist pattern to the resist underlayer film. Furthermore, the present inventors believe that as a result of the improved adhesion, even a thinner resist pattern is less likely to collapse, making it possible to form a finer resist pattern.

[0011] <Polymer (A)> The polymer (A) has a partial structure represented by the following formula (A). (In formula (A), R １１ represents an (n+2)-valent group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. １２ represents a hydrogen atom, or an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, two R １２may be the same or different. * represents a bond.)

[0012] The bond in formula (A) is preferably bonded to a carbon atom.

[0013] The polymer (A) preferably has a structural unit represented by the following formula (A-11): For example, the partial structure represented by formula (A) is a part of the structural unit represented by the following formula (A-11). (In formula (A-11), A １ , A ２ , A ３ , A ４ , A ５ and A ６ R each independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ represents an (n+2)-valent organic group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. １２ represents a hydrogen atom, or an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, two R １２ may be the same or different.)

[0014] <<R １１ >> In formula (A) and formula (A-11), R １１represents an (n+2)-valent organic group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The number of carbon atoms in the (n+2)-valent organic group is not particularly limited, but is preferably 4 to 30, more preferably 4 to 20, and particularly preferably 4 to 15. Examples of aromatic hydrocarbon rings in the (n+2)-valent organic group include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of aliphatic hydrocarbon rings include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. The aliphatic hydrocarbon ring may have a polycyclic structure. The aliphatic hydrocarbon ring may or may not have an unsaturated bond. The aliphatic hydrocarbon ring may be an aliphatic hydrocarbon ring constituting a bridged polycyclic structure. The bridged polycyclic structure may have a heteroatom as an atom constituting the polycyclic structure. Examples of heteroatoms include an oxygen atom and a nitrogen atom. Examples of bridged polycyclic structures include a norbornene ring.

[0015] R １１ Examples of the trivalent organic group include the following: The following trivalent organic groups may be substituted with an alkyl group, an alkylcarbonyl group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a combination of two or more thereof. In each of the following formulas, * represents a bond.

[0016] The trivalent organic group is preferably a trivalent organic group represented by the following formula: (wherein q represents an integer of 0 to 3, R ２ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. However, when q represents 2 or 3, R ２ may be the same or different. * represents a bond.)

[0017] R １１ Examples of the tetravalent organic group include the following: (In formulas (x-1) to (x-11), R １ ~R ４R each independently represents a hydrogen atom, a halogen atom, 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, a monovalent organic group having 1 to 6 carbon atoms and a fluorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group. * represents a bond.

[0018] (In formulas (X3-1) and (X3-2), x and y each independently represent a single bond, an ether bond, a carbonyl group, an ester bond, an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, a sulfonyl bond, or an amide group. j and k are integers of 0 or 1. * represents a bond.)

[0019] * represents a bond.

[0020] The tetravalent organic group represented by formula (X3-1) or (X3-2) may have a structure represented by any one of the following formulas (X3-3) to (X3-19). * represents a bond.

[0021] <<R １２ >> In formula (A) and formula (A-11), R １２ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 13 carbon atoms. The alkyl group having 1 to 13 carbon atoms may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms.

[0022] As the alkyl group having 1 to 13 carbon atoms, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the alkoxy group having 1 to 13 carbon atoms, an alkoxy group having 1 to 8 carbon atoms is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred. As the alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 8 carbon atoms is preferred, and an alkylcarbonyloxy group having 2 to 6 carbon atoms is more preferred. As the alkoxycarbonyl group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms is preferred, and an alkoxycarbonyl group having 2 to 6 carbon atoms is more preferred. As the alkylthio group having 1 to 13 carbon atoms, an alkylthio group having 1 to 8 carbon atoms is preferred, and an alkylthio group having 1 to 6 carbon atoms is more preferred. As the alkylsulfonyloxy group having 1 to 13 carbon atoms, an alkylsulfonyloxy group having 1 to 8 carbon atoms is preferred, and an alkylsulfonyloxy group having 1 to 6 carbon atoms is more preferred. As the alkoxysulfonyl group having 1 to 13 carbon atoms, an alkoxysulfonyl group having 1 to 8 carbon atoms is preferred, and an alkoxysulfonyl group having 1 to 6 carbon atoms is more preferred.

[0023] As used herein, the alkyl group is not limited to a linear one, but may also be branched or cyclic. Examples of linear or branched alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an n-hexyl group. Examples of cyclic alkyl groups (cycloalkyl groups) include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. As used herein, examples of alkoxy groups include a methoxy group, an ethoxy group, an n-pentyloxy group, and an isopropoxy group. As used herein, examples of alkylcarbonyloxy groups include a methylcarbonyloxy group and an ethylcarbonyloxy group. As used herein, examples of alkoxycarbonyl groups include a methoxycarbonyl group, an ethoxycarbonyl group, and an isopropoxycarbonyl group. As used herein, examples of alkylthio groups include a methylthio group, an ethylthio group, an n-pentylthio group, and an isopropylthio group. As used herein, examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl groups. As used herein, examples of alkynyl groups include groups in which the double bond of the alkenyl groups listed above for "alkenyl groups" is replaced with a triple bond. As used herein, examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0024] R １２ From the viewpoint of suitably achieving the effects of the present invention, the alkyl group is preferably an alkyl group having 1 to 13 carbon atoms or an alkyl group having 1 to 13 carbon atoms substituted with an alkoxy group having 1 to 13 carbon atoms.

[0025] When n is 2, two R １２are preferably the same. <<Q>> In formula (A-11), Q represents a divalent organic group. The divalent organic group is not particularly limited, but is preferably a divalent organic group having a heteroatom, and more preferably a divalent organic group having a nitrogen atom and an oxygen atom. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of carbon atoms in the divalent organic group is not particularly limited, but is preferably 3 to 30, and more preferably 3 to 20.

[0026] From the viewpoint of suitably obtaining the effects of the present invention, Q is preferably represented by either formula (A-21) or formula (A-22) below. (In formula (A-21), X １ represents a divalent group represented by the following formula (A-21-1), (A-21-2) or (A-21-3). １ and Z ２ Each of Q independently represents a single bond or a divalent group represented by the following formula (A-21-4). * represents a bond. １ represents a divalent group having an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * represents a bond. (In formulas (A-21-1) to (A-21-3), R １ ~R ５ R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted 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. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ and R ４may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom. (In formula (A-21-4), m1 is an integer of 1 to 4, m2 is 0 or 1, *3 represents a bond bonded to a nitrogen atom, and *4 represents a bond bonded to a carbon atom.)

[0027] Q in formula (A-22) １ is preferably represented by any one of the following formulas (A-22-1) to (A-22-4). (In formulas (A-22-1) to (A-22-4), R ３１ ~R ３６ each independently represents a halogen atom, a hydroxy 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 bond. In formula (A-22-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer of 0 to 4. When n3 is 1, n11 represents an integer of 0 to 6. R ３１ When is 2 or more, R is 2 or more ３１ In formula (A-22-2), Z may be the same or different. １ 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. R ３２ When is 2 or more, R is 2 or more ３２ may be the same or different. ３３ When is 2 or more, R is 2 or more ３３ In formula (A-22-3), Y may be the same or different. １ and Y ２ each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. R３４ When is 2 or more, R is 2 or more ３４ In formula (A-22-4), Z may be the same or different. ２ 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. R ３５ When is 2 or more, R is 2 or more ３５ may be the same or different. ３６ When is 2 or more, R is 2 or more ３６ may be the same or different.)

[0028] Examples of Q in formula (A-11) include the following structures. * represents a bond.

[0029] When the polymer (A) has a structural unit represented by formula (A-11), the mass proportion of the structural unit represented by formula (A-11) in the polymer (A) is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

[0030] The method for producing polymer (A) is not particularly limited, and examples thereof include a method of reacting at least one of a tetracarboxylic dianhydride represented by formula (A1) below and a tricarboxylic anhydride represented by formula (A2) below with a diepoxy compound represented by formula (2A) below and a compound represented by formula (C) below. In this case, polymer (A) having a structural unit represented by formula (A-11) is obtained. For example, at least one of a tetracarboxylic dianhydride represented by formula (A1) below and a tricarboxylic anhydride represented by formula (A2) below and a diepoxy compound represented by formula (2A) below are dissolved in an appropriate molar ratio in an organic solvent containing a large excess of a compound represented by formula (C) below. Then, polymer (A) is obtained by polymerization in the presence of a catalyst that activates the epoxy group. Note that R １２ is a hydrogen atom, the compound represented by formula (C) is not used, and another inert organic solvent is used. In the above reaction, a tetracarboxylic acid or a tricarboxylic acid may be used instead of the tetracarboxylic dianhydride represented by formula (A1) and the tricarboxylic anhydride represented by formula (A2).

[0031] Examples of catalysts that activate epoxy groups include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10% by mass based on the total mass of the polymer raw materials used in the reaction. Optimal conditions for the temperature and time of the polymerization reaction can be selected, for example, from the ranges of 80 to 160°C and 2 to 50 hours.

[0032] (In formula (A1) and formula (A2), R １１ is R in formula (A-11). １１ is synonymous with

[0033] (In formula (2A), A １ , A ２ , A ３ , A ４ , A ５ , A６ and Q are A in formula (A-11), respectively. １ , A ２ , A ３ , A ４ , A ５ , A ６ and Q.)

[0034] (In formula (C), R １２ is R in formula (A-11). １２ is synonymous with

[0035] Examples of the compound represented by formula (C) include the following compounds.

[0036] The molecular weight of the polymer (A) is not particularly limited. The lower limit of the weight average molecular weight of the polymer (A) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight average molecular weight of the polymer (A) is, for example, 100,000, 75,000, or 50,000.

[0037] The content of the polymer (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 45% by mass, based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0038] <Polymer (B)> The polymer (B) has a polymerizable multiple bond. The polymerizable multiple bond is, for example, one or more types of polymerizable multiple bonds selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, and a carbon-nitrogen triple bond. The polymer (B) may have the polymerizable multiple bond in its main chain, or in its side chain, for example. The polymer (B) is a different polymer from the polymer (A).

[0039] The polymer (B) is an organic polymer. The polymer (B) may be a homopolymer or a copolymer.

[0040] The polymer (B) has, in its side chain, a group having a polymerizable multiple bond, such as a (meth)acryloyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, an allyl group, etc. The polymer (B) has, in its main chain or side chain, a vinyl group (—CH═CH—), as the group having a polymerizable multiple bond.

[0041] From the viewpoint of suitably achieving the effects of the present invention, the polymer (B) is preferably a polymer (B-1) having a structural unit represented by formula (B-1) described below. From the viewpoint of suitably achieving the effects of the present invention, the polymer (B) is preferably a polymer (B-2) having a structural unit represented by formula (B-2) described below.

[0042] <<Polymer (B-1)>> The polymer (B-1) is, for example, a polymer obtained by polymerizing a polymerizable unsaturated bond of a compound having a group having a polymerizable unsaturated bond. The polymer (B-1) may be a homopolymer or a copolymer. Examples of the group having a polymerizable unsaturated bond include a (meth)acryloyl group, a vinylaryl group (for example, a styryl group), a vinyloxy group, and an allyl group.

[0043] For example, in polymer (B-1), the polymerizable multiple bond is bonded to the main chain of polymer (B-1) via a linking group having a structure obtained by reacting an epoxy group with a nucleophilic functional group. Examples of the nucleophilic functional group include one or more selected from the group consisting of a carboxy group, a hydroxy group, an amino group, and a thiol group. The hydroxy group may or may not be a phenolic hydroxy group. When an epoxy group reacts with a carboxy group, the reaction proceeds as follows, forming the following structure (S1): (In the formula, * represents a bond.)

[0044] Furthermore, for example, in polymer (B-1), the polymerizable multiple bond is bonded to the main chain of polymer (B-1) via a linking group having a structure obtained by reaction of an isocyanate group with a nucleophilic functional group. In this case, the nucleophilic functional group may be, for example, one or more selected from the group consisting of a hydroxy group, an amino group, and a thiol group. The hydroxy group may or may not be a phenolic hydroxy group.

[0045] The polymer (B-1) has a structural unit represented by the following formula (B-1). (In formula (B-1), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ represents a single bond or a linking group. ２ represents the monovalent group having a polymerizable multiple bond.

[0046] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group. cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include a 3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, a 2-ethyl-3-methylcyclopropyl group, an n-heptyl group, a cycloheptyl group, a norbornyl group, an n-octyl group, a cyclooctyl group, an n-nonyl group, an isobornyl group, a tricyclononyl group, an n-decyl group, an adamantyl group, and a tricyclodecyl group. Of these, a methyl group is preferred.

[0047] L １ When L is a linking group, the number of carbon atoms in the linking group is not particularly limited, but may be, for example, 1 to 10. １ is a linking group, examples of the linking group include a linking group having a structure obtained by reacting an epoxy group with a nucleophilic functional group, and a linking group having a structure obtained by reacting an isocyanate group with a nucleophilic functional group.

[0048] L １ Examples of the linking groups include the following linking groups (L1-1) to (L1-11). (wherein *1 represents R in formula (B-1) １ *2 represents a bond bonded to a carbon atom bonded to L in formula (B-1). ２ represents a bond bonded to

[0049] L ２ is a monovalent group having a polymerizable multiple bond. The monovalent group may be the polymerizable multiple bond itself. The number of carbon atoms in the monovalent group is not particularly limited, but may be, for example, 1 to 20 or 1 to 10.

[0050] L ２ Examples of the group include the following monovalent groups (L2-1) to (L2-81). (In the formula, * represents a bond.)

[0051] Examples of combinations of the linking groups (L1-1) to (L1-9) and the monovalent groups (L2-1) to (L2-7) include the following combinations.・Combination of (L1-1) and (L2-1) ・Combination of (L1-1) and (L2-2) ・Combination of (L1-1) and (L2-7) ・Combination of (L1-2) and (L2-3) ・Combination of (L1-2) and (L2-4) ・Combination of (L1-2) and (L2-7) ・Combination of (L1-3) and (L2-3) ・Combination of (L1-3) and (L2-4) ・Combination of (L1-4) and (L2-7) ・Combination of (L1-5) and (L2-1) ・Combination of (L1-5) and (L2-2) ・Combination of (L1-6) and (L2-1) ・Combination of (L1-6) and (L2-2) ・Combination of (L1-7) and (L2-5) A combination of (L1-7) and (L2-6) A combination of (L1-8) and (L2-7) A combination of (L1-9) and (L2-7) The combination of (L1-1) and (L2-1) is synonymous with the combination of (L1-2) and (L2-3). The combination of (L1-1) and (L2-2) is synonymous with the combination of (L1-2) and (L2-4).

[0052] In addition, L in the structural unit represented by formula (B-1) １ -L ２ Preferably, the compound has a structure represented by the following formula (1a), (1b) or (1c): (In formulas (1a) to (1c), R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. *a and *b represent bonds, with *a being on the main chain side of polymer (B-1) and *b being on the terminal side of the side chain of polymer (B-1). *b may also be a bond to a hydrogen atom.

[0053] Examples of the structural unit represented by formula (B-1) include the following structural units.

[0054] An example of the polymer (B-1) having a structural unit represented by formula (B-1) can be obtained, for example, by reacting a glycidyl (meth)acrylate polymer with a compound (C1) having a polymerizable multiple bond and a carboxy group, as shown below. The glycidyl (meth)acrylate polymer may be a homopolymer or a copolymer. Examples of the copolymer include a copolymer of glycidyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, and a copolymer of glycidyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0055] (In the formula, R １ , and L ２ respectively represent R in formula (B-1). １ , and L ２ is synonymous with

[0056] The reaction can be carried out in the presence of a catalyst such as tetrabutylphosphonium bromide.

[0057] Examples of the compound (C1) having a polymerizable multiple bond and a carboxy group include acrylic acid, methacrylic acid, 4-vinylbenzoic acid, sorbic acid, tetrolic acid, tiglic acid, 1-cyclohexene-1-carboxylic acid, 2-benzylacrylic acid, trans-cinnamic acid, trans-4-methoxycinnamic acid, α-phenylcinnamic acid, monomethyl fumarate, α-cyanocinnamic acid, 4-nitrocinnamic acid, and 3-nitrocinnamic acid.

[0058] Another example of the polymer (B-1) having a structural unit represented by formula (B-1) can be obtained, for example, by reacting a (meth)acrylate polymer having a hydroxy group with a compound (C2) having a polymerizable multiple bond and an isocyanate group, as shown below. The (meth)acrylate polymer having a hydroxy group may be a homopolymer or a copolymer. (In the formula, R １ , and L ２ respectively represent R in formula (B-1). １ , and L ２ It is synonymous with R １１represents a divalent organic group. １２ represents a single bond or a divalent organic group. １１ is, for example, an alkylene group having 1 to 4 carbon atoms. １２ is, for example, a single bond or an alkylene group having 1 to 4 carbon atoms.

[0059] Another example of the polymer (B-1) having a structural unit represented by formula (B-1) can be obtained, for example, by reacting a styrene-based polymer having a hydroxy group or an amino group with a compound (C2) having a polymerizable multiple bond and an isocyanate group, as shown below. The styrene-based polymer having a hydroxy group or an amino group may be a homopolymer or a copolymer. (In the formula, R １ , and L ２ respectively represent R in formula (B-1). １ , and L ２ It is synonymous with R １２ represents a single bond or a divalent organic group. １２ is, for example, a single bond or an alkylene group having 1 to 4 carbon atoms.

[0060] Examples of the compound (C2) having a polymerizable multiple bond and an isocyanate group include the following compounds.

[0061] The polymer (B-1) may have a structural unit other than the structural unit represented by formula (B-1). Examples of such a structural unit include a structural unit represented by formula (B-12) below, a structural unit represented by formula (B-13) below, and a structural unit represented by formula (B-14) below. (In formula (B-12), R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; L ３ represents a monovalent group having 1 to 20 carbon atoms. ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Ar represents a benzene ring or a naphthalene ring, L ４ is a hydroxy group, a cyano group, a nitro group, or an amino group (-NH ２ ) represents. ５represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. m1 represents an integer of 0 to 3. m2 represents an integer of 0 to 5, provided that the sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L ４ may be the same or different. When m2 is 2 to 5, multiple L ５ may be the same or different. ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; L ６ represents a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.

[0062] L in formula (B-12) ３ The monovalent group having 1 to 20 carbon atoms represents, for example, a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group. In addition, the alkyl group may have an oxygen atom inserted between carbon atoms. In addition, L ３ Examples of the monovalent group having 1 to 20 carbon atoms include groups represented by the following formula (2-1): (In formula (2-1), L ３ａ represents an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted aromatic hydrocarbon group. ３ａ Examples of the aromatic hydrocarbon group in L include a phenyl group and a naphthyl group. ３ａ Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom and a hydroxy group. The number of substituents may be one or more. When there are more than one substituent, the multiple substituents may be the same or different. ３ａExamples of the substituent in the optionally substituted aromatic hydrocarbon group include a halogen atom, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom. The number of substituents may be one or more. When there are multiple substituents, the multiple substituents may be the same or different.

[0063] R ２ an alkyl group having 1 to 10 carbon atoms represented by the formula: ３ and L ６ Specific examples of the alkyl group having 1 to 10 carbon atoms represented by are as described above. ５ Examples of the halogen atom in L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ５ Examples of the alkyl group having 1 to 6 carbon atoms in the formula (L) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, and an i-butyl group. ５ Examples of the alkoxy group having 1 to 6 carbon atoms in the formula (I) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. m1 represents an integer of 0 to 3 and may be 0, 1, 2, or 3. m2 represents an integer of 0 to 5 and may be 0, 1, 2, 3, 4, or 5.

[0064] L ３ and L ６Examples of the aryl group having 6 to 40 carbon atoms represented by L include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. ６ Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0065] Examples of the monomer used to derive the formula (B-12) include the following compounds:

[0066] Examples of the monomer used to derive the formula (B-13) include the following compounds: Me represents a methyl group.

[0067] Examples of the monomer used to derive the formula (B-14) include the following compounds:

[0068] The proportion of the structural units represented by formula (B-1) in polymer (B-1) is not particularly limited, but the molar ratio of the structural units represented by formula (B-1) to all structural units of polymer (B-1) may be, for example, 20 mol% to 100 mol%, 40 mol% to 100 mol%, or 60 mol% to 100 mol%. The proportion of the total (S) of the structural units represented by formula (B-12), formula (B-13), and formula (B-14) in polymer (B-1) is not particularly limited, but the molar ratio of the total (S) to all structural units of polymer (B-1) may be, for example, 0 mol% to 80 mol%, or more than 0 mol% but not more than 60 mol%.

[0069] The polymer (B-1) may contain structural units other than the structural units represented by formula (B-1), the structural units represented by formula (B-12), the structural units represented by formula (B-13), and the structural units represented by formula (B-14). In such cases, the molar ratio of the other structural units to all structural units of the polymer (B-1) is, for example, more than 0 mol % and not more than 20 mol %.

[0070] <<Polymer (B-2)>> The polymer (B-2) has a structural unit represented by the following formula (B-2). (In formula (B-2), 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; Q ２１ represents a divalent organic group. ２１ represents the divalent group having a polymerizable multiple bond.

[0071] Q ２１ Specific and preferred examples of include specific and preferred examples of Q in formula (A-11).

[0072] R ２１ The polymerizable multiple bond contained in R is preferably a carbon-carbon double bond. ２１ The number of carbon atoms in R is, for example, 2 to 10.２１ may or may not have a heteroatom. ２１ may be a divalent hydrocarbon group. ２１ Examples of such structures include the following: (* represents a bond.)

[0073] The mass proportion of the structural unit represented by formula (B-2) in polymer (B-2) is not particularly limited, but is preferably 50 mass% to 100 mass%, more preferably 75 mass% to 100 mass%, and particularly preferably 90 mass% to 100 mass%.

[0074] The method for producing the polymer (B-2) is not particularly limited, but examples thereof include a method of reacting a dicarboxylic acid represented by the following formula (1B) with a diepoxy compound represented by the following formula (2B):

[0075] Examples of catalysts that activate epoxy groups include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10% by mass based on the total mass of the polymer raw materials used in the reaction. Optimal conditions for the temperature and time of the polymerization reaction can be selected, for example, from the ranges of 80 to 160°C and 2 to 50 hours.

[0076] (In formula (1B), R ２１ is R in formula (B-2) ２１ is synonymous with

[0077] (In formula (2B), A １１ , A １２ , A １３ , A １４ , A １５ , A １６ and Q ２１ are A in formula (B-2), respectively. １１ , A １２ , A １３ , A １４ , A １５ , A １６and Q ２１ is synonymous with

[0078] The molecular weight of the polymer (B) is not particularly limited. The lower limit of the weight average molecular weight of the polymer (B) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight average molecular weight of the polymer (B) is, for example, 100,000, 50,000, or 30,000.

[0079] The content of the polymer (B) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 45% by mass, based on the film-constituting components.

[0080] The mass ratio of the polymer (A) to the polymer (B) (polymer (A):polymer (B)) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40.

[0081] The total content of the polymer (A) and the polymer (B) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 100% by mass, more preferably 50% by mass to 95% by mass, and particularly preferably 60% by mass to 90% by mass, based on the film-constituting components.

[0082] <Solvent (C)> The solvent (C) is not particularly limited and may be water or an organic solvent. Examples of the organic solvent include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0083] Examples of the alkylene group of the alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8. Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0084] Examples of the alkylene group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the monocarboxylic acid of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include those having 5 to 10 carbon atoms. Examples of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0085] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0086] Among these solvents (C), alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0087] These solvents (C) may be used alone or in combination of two or more.

[0088] The mass proportion of the organic solvent in the solvent (C) is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0089] The content of the solvent (C) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.

[0090] <Crosslinking Agent (D)> The crosslinking agent (D) is not particularly limited. The crosslinking agent (D) has a structure different from that of the polymer (A) and the polymer (B).

[0091] The crosslinking agent (D) is preferably an aminoplast crosslinking agent or a phenoplast crosslinking agent. The aminoplast crosslinking agent is an addition condensation product of a compound having an amino group, such as melamine or guanamine, with formaldehyde. The phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxy group with formaldehyde.

[0092] Examples of the crosslinking agent (D) include compounds having two or more of the following structures: (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0093] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0094] The crosslinking agent (D) is preferably a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group, which may be used alone or in combination of two or more.

[0095] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0096] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0097] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0098] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0099] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0100] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0101] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0102] (In formula (3d), R １ represents a methyl group or an ethyl group.

[0103] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0104] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0105] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. １ is 1≦n １ an integer ≦3, n ２ is 2≦n ２ an integer ≦5, n ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n５ an integer ≦3, n ６ is 1≦n ６ n is an integer ≦4 ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0106] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ an integer ≦5, n １１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0107] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0108] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0109] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0110] The molecular weight of the crosslinking agent (D) is not particularly limited, but is preferably 500 or less.

[0111] The content of the crosslinking agent (D) in the composition for forming a resist underlayer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, based on the total amount of the polymer (A) and the polymer (B).

[0112] <Curing Catalyst (E)> The curing catalyst (E) contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0113] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0114] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal 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-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0115] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0116] 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.

[0117] The curing catalyst (E) may be used alone or in combination of two or more.

[0118] When the curing catalyst (E) is used, the content of the curing catalyst (E) relative to the crosslinking agent (D) is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0119] <Other Components> A surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface irregularities.

[0120] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more.

[0121] The composition for forming a resist underlayer film may contain a polymerization inhibitor (radical trapping agent) as necessary. Examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and 4-methoxy-1-naphthol. The content of the polymerization inhibitor in the composition for forming a resist underlayer film is not particularly limited, but is preferably 1 mass % or less based on the solid content.

[0122] The solid content of the composition for forming a resist underlayer film of the present invention, that is, the content of components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.

[0123] The composition for forming a resist underlayer film is preferably used for EUV lithography.The composition for forming a resist underlayer film is preferably used for forming an underlayer film of a metal-containing resist.

[0124] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the composition for forming a resist underlayer film described above. The resist underlayer film can be produced, for example, by applying the composition for forming a resist underlayer film described above onto a semiconductor substrate and baking the applied composition.

[0125] Examples of semiconductor substrates onto which the resist underlayer film-forming composition can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0126] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0127] The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate by a suitable application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. A baking temperature of 120°C to 350°C and a baking time of 0.5 to 30 minutes are preferred, and a baking temperature of 150°C to 300°C and a baking time of 0.8 to 10 minutes are more preferred.

[0128] The thickness of the resist underlayer film may be, 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 ( 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0129] The method for measuring the film thickness of the resist underlayer film in this specification is as follows: Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Corporation) SWE (single wavelength ellipsometer) mode Arithmetic mean of 8 points (for example, measuring 8 points at 1 cm intervals in the X direction of the wafer)

[0130] (Laminate) The laminate of the present invention includes a semiconductor substrate and the resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrates described above. The resist underlayer film is disposed on the semiconductor substrate, for example.

[0131] (Method for manufacturing a semiconductor element, method for forming a pattern) The method for manufacturing a semiconductor element of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and forming a resist film on the resist underlayer film.

[0132] The pattern forming method of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, forming a resist film on the resist underlayer film, irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern, and etching the resist underlayer film using the resist pattern as a mask.

[0133] Typically, a resist film is formed on the resist underlayer film. The film thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0134] The resist film formed on the resist underlayer film by a known method (e.g., coating and baking a resist composition) is not particularly limited as long as it is responsive to light or electron beam (EB) irradiation. Both negative and positive photoresists can be used. In this specification, resists responsive to EB are also referred to as photoresists. Examples of photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include 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).

[0135] Also, 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, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0136] Examples of the resist composition include the following compositions.

[0137] An actinic ray-sensitive or radiation-sensitive resin composition comprising: Resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (121):

[0138] In the general formula (121), m represents an integer of 1 to 6. １ and R ２ each independently represents a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ - or -SO ３ - represents. ２ represents an alkylene group which may have a substituent or a single bond. １ represents a cyclic organic group which may have a substituent. ＋ represents a cation.

[0139] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to Periods 3 to 7 of Groups 3 to 15 of the periodic table.

[0140] 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) containing an acid-dissociable group; and an acid generator.

[0141] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ is a hydroxy 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, multiple R １ are the 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 containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R ４is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0142] A resist composition comprising: a resin (A1) containing 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.

[0143] [In the formula, R ２ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X １ represents a single bond, —CO—O—*, or —CO—NR ４ -*, * represents a bond to -Ar, R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxy group and a carboxy group.]

[0144] Examples of the resist film include the following.

[0145] A resist film comprising a base resin comprising a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain upon exposure:

[0146] (In formula (a1) and formula (a2), R Ａ are each independently a hydrogen atom or a methyl group. １ and R ２ are each independently a tertiary alkyl group having 4 to 6 carbon atoms. ３ are each independently a fluorine atom or a methyl group, and m is an integer of 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 containing 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.

[0147] Examples of resist materials include the following:

[0148] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2):

[0149] (In formula (b1) and formula (b2), R Ａ 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 some of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group; and X ２ At least one hydrogen atom contained in X is substituted with 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 some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. １ and Rf ２ may combine to form a carbonyl group. １ ~R ５ are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and in which some 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 ester group. １ and R ２may be bonded to form a ring together with the sulfur atom to which they are attached.

[0150] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0151] (In formula (a), R Ａ is a hydrogen atom or a methyl group. １ is a hydrogen atom or an acid labile group. ２ 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, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. ２ is -O-, -O-CH ２ - or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. However, m+u is an integer of 1 to 4.

[0152] A resist composition that generates an acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising: a base component (A) whose solubility in a developer changes due to the action of the acid; and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) comprises a fluororesin component (F1) that has a structural unit (f1) that includes a base dissociable group, and a structural unit (f2) that includes a group represented by the following general formula (f2-r-1):

[0153] [In formula (f2-r-1), Rf ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0154] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0155] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ represents a divalent aromatic cyclic group which may have a substituent. ０１ is a single bond or a divalent linking group. ２ are each independently an organic group having a fluorine atom.

[0156] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738.

[0157] A coating comprising a metal oxo-hydroxo network having organic ligands with metal carbon and / or metal carboxylate bonds.

[0158] Inorganic oxo / hydroxo-based compositions.

[0159] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures thereof, where R and R′ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and a hydrolyzable metal compound having 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.

[0160] an organic solvent and a solution of the formula RSnO （３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0161] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0162] Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0163] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0164] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0165] Irradiation with light or electron beams is carried out, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. The composition for forming a resist underlayer film of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, more preferably for EUV (extreme ultraviolet) exposure. The irradiation energy of the electron beam and the exposure dose of light are not particularly limited.

[0166] After irradiation with light or electron beams and before development, baking (PEB: Post Exposure Bake) may be performed. The baking temperature is not particularly limited, but is preferably 60° C. to 150° C., more preferably 70° C. to 120° C., and particularly preferably 75° C. to 110° C. The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0167] For example, an alkaline developer or an organic solvent is used for development. The development temperature is, for example, 5°C to 50°C. The development time is, for example, 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, the aqueous solutions of the alkalis may be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like may also be added to these developers. Alternatively, development may be carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the portions of the photoresist where the alkaline dissolution rate is not improved may be developed.

[0168] An organic solvent can be used as a developer for the metal-containing resist, and development is carried out with the developer (solvent) after irradiation with light or electron beams. As a result, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed areas is removed, and a pattern of the metal-containing resist film is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methyl ... -Methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3 -methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate,Examples of the developer include propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can also be added to these developers.

[0169] 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. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. If the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the semiconductor substrate is processed by a known method (e.g., dry etching), thereby manufacturing a semiconductor device.

[0170] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0171] The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 9 below are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40°C Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0172] Synthesis Example 1 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.45 g of diethylbarbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 56.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by reflux heating for 10 hours to obtain a solution containing polymer 1. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 10,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0173]

[0174] Synthesis Example 2 7.00 g of Denacol Ex711 (manufactured by Nagase ChemteX Corporation), 5.61 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 51.70 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 24 hours to obtain a solution containing polymer 2. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. GPC analysis showed that the polymer in the obtained solution had a weight average molecular weight of 12,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1c) and (1d).

[0175]

[0176] Synthesis Example 3 7.00 g of Denacol Ex201 (manufactured by Nagase ChemteX Corporation), 6.86 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.20 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 32.81 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out by heating at 130°C for 24 hours to obtain a solution containing polymer 3. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 19,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (1e) and (1d).

[0177]

[0178] Synthesis Example 4 7.00 g of Denacol Ex711 (manufactured by Nagase ChemteX Corporation), 4.97 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.31 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 49.11 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 24 hours to obtain a solution containing Polymer 4. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 16,000 in terms of standard polystyrene. The polymer obtained in this Synthesis Example has structural units represented by the following formulas (1c) and (1f).

[0179]

[0180] Synthesis Example 5 7.00 g of Denacol Ex201 (manufactured by Nagase ChemteX Corporation), 6.17 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.76 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 55.71 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out by heating at 100°C for 24 hours to obtain a solution containing Polymer 5. The polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 31,000 in terms of standard polystyrene. The polymer obtained in this Synthesis Example had structural units represented by the following formulas (1e) and (1f).

[0181]

[0182] Synthesis Example 6 20.00 g of polyglycidyl methacrylate (Maruzen Petrochemical Co., Ltd.), 4.88 g of sorbic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 16.77 g of propylene glycol monomethyl ether and 2.58 g of propylene glycol monomethyl ether acetate. The reaction vessel was then purged with nitrogen and heated to 100°C for 24 hours to obtain a solution containing polymer 6. The polymer solution did not become cloudy even when cooled to room temperature, and exhibited good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 25,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1g).

[0183]

[0184] Synthesis Example 7 20.00 g of polyglycidyl methacrylate (Maruzen Petrochemical Co., Ltd.), 3.75 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 15.07 g of propylene glycol monomethyl ether and 0.88 g of propylene glycol monomethyl ether acetate. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was heated to 100°C for 24 hours to obtain a solution containing Polymer 7. The polymer solution did not become cloudy even when cooled to room temperature, and exhibited good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 21,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1h).

[0185]

[0186] Synthesis Example 8 20.00 g of polyglycidyl methacrylate (Maruzen Petrochemical Co., Ltd.), 3.28 g of acrylic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 14.36 g of propylene glycol monomethyl ether and 0.17 g of propylene glycol monomethyl ether acetate. The reaction vessel was purged with nitrogen, and the mixture was heated to 100°C for 24 hours to obtain a solution containing polymer 8. The polymer solution did not become cloudy even when cooled to room temperature, and exhibited good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 21,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1i).

[0187]

[0188] Synthesis Example 9 20.00 g of polyglycidyl methacrylate (Maruzen Petrochemical Co., Ltd.), 3.66 g of tetrolic acid (Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 14.93 g of propylene glycol monomethyl ether and 0.74 g of propylene glycol monomethyl ether acetate. The reaction vessel was then purged with nitrogen and heated to 100°C for 24 hours to obtain a solution containing polymer 9. The polymer solution did not become cloudy even when cooled to room temperature, and exhibited good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis revealed that the polymer in the obtained solution had a weight average molecular weight of 21,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1j).

[0189]

[0190] [Preparation of Compositions for Forming Resist Underlayer Films] (Examples and Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 9 above were mixed in the proportions shown in Table 1, and the mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare compositions for forming resist underlayer films of Examples 1 to 7 and Comparative Examples 1 to 3, respectively.

[0191] The abbreviations in Table 1 are as follows: PL-LI: tetramethoxymethyl glycoluril PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- (structural formula below)

[0192] Py-PSA: Pyridinium-p-hydroxybenzenesulfonic acid PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0193]

[0194] [Elution Test in Photoresist Solvent] Each of the resist underlayer film-forming compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied to a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer film (film thickness 5 nm). These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio), which is a solvent used in photoresists. A change in film thickness of less than 5 Å was rated as "good" and a change in film thickness of 5 Å or more was rated as "poor." The results are shown in Table 2.

[0195]

[0196] [Resist Pattern Formation Test Using Electron Beam Lithography Apparatus] The resist underlayer film-forming compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were each applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a 5 nm-thick resist underlayer film. An EUV positive resist solution was spin-coated onto the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was irradiated with EB under specified conditions using an electron beam lithography apparatus (ELS-G130). After irradiation, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer. Resist patterns with line sizes of 16 nm to 28 nm were formed. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the length of the resist pattern. The photoresist pattern thus obtained was evaluated for the possibility of forming 22 nm lines and spaces (L / S). Formation of a 22 nm L / S pattern was confirmed. The charge amount required to form 22 nm lines / 44 nm pitch (line and space (L / S = 1 / 1)) was defined as the optimal irradiation energy, and the irradiation energy (μC / cm ２) are shown in Table 3. The minimum CD size is the limit CD size at which no pattern collapse occurs, and is shown in Table 3. Improvements in the minimum CD size were confirmed in Examples 1 to 7 compared to Comparative Examples 1 to 3.

[0197]

Claims

1. A resist underlayer film-forming composition comprising a polymer (A) having a partial structure represented by the following formula (A), a polymer (B) having a polymerizable multiple bond, and a solvent (C). (In formula (A), R １１ represents a (n + 2)-valent group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. R １２ represents a hydrogen atom, or an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms. n represents 1 or 2. When n is 2, the two R １２ may be the same or different. * represents a bond.) 2. The resist underlayer film-forming composition according to claim 1, wherein the polymer (B) is a polymer (B-1) having a structural unit represented by the following formula (B-1) or a polymer (B-2) having a structural unit represented by the following formula (B-2). (In formula (B-1), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L １ represents a single bond or a linking group. L ２ represents a monovalent group having the polymerizable multiple bond.) (In formula (B-2), A １１ , A １２ , A １３ , A １４ , A １５ and A １６ each independently represent a hydrogen atom, a methyl group or an ethyl group, and Q ２１ represents a divalent organic group. R ２１ represents a divalent group having the polymerizable multiple bond.) 3. L in the structural unit represented by the formula (B-1) １ -L ２ has a structure represented by the following formula (1a), (1b) or (1c), and the resist underlayer film-forming composition according to claim 2. (In the formulas (1a) to (1c), R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. *a and *b represent a bond, *a is on the main chain side of the polymer (B-1), and *b is on the terminal side of the side chain of the polymer (B-1).) 4. The resist lower layer film-forming composition according to claim 1, wherein the polymer (A) has a structural unit represented by the following formula (A-11). (In formula (A-11), A １ , A ２ , A ３ , A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group or an ethyl group, and Q represents a divalent organic group. R １１ represents an (n + 2)-valent organic group having at least one of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. R １２ represents a hydrogen atom, or an alkoxy group having 1 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylthio group having 1 to 13 carbon atoms, a nitro group, an alkylsulfonyloxy group having 1 to 13 carbon atoms, and an alkoxysulfonyl group having 1 to 13 carbon atoms, and represents an alkyl group having 1 to 13 carbon atoms which may be substituted with at least one group selected from the group consisting of. n represents 1 or 2. When n is 2, the two R １２ may be the same or different.) 5. The resist underlayer film-forming composition according to claim 4, wherein Q in the formula (A-11) is represented by any one of the following formula (A-21) and formula (A-22). (In formula (A-21), X １ represents a divalent group represented by the following formula (A-21-1), the following formula (A-21-2), or the following formula (A-21-3). Z １ and Z ２ each independently represent a single bond or a divalent group represented by the following formula (A-21-4). * represents a bond. In formula (A-22), Q １ represents a divalent group having an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * represents a bond.) (In formulas (A-21-1) to (A-21-3), R １ to R ５ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted 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. R １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. R ３ and R ４ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom.) (In formula (A-21-4), m1 is an integer of 1 to 4, and m2 is 0 or 1. *3 represents a bond bonded to a nitrogen atom. *4 represents a bond bonded to a carbon atom.) 6. Q in the formula (A-22) １ The resist underlayer film-forming composition according to claim 5, wherein Q is represented by any one of the following formulas (A-22-1) to (A-22-4). (In the formulas (A-22-1) to (A-22-4), R ３１ to R ３６ each independently represents a halogen atom, a hydroxy 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 bond. In the formula (A-22-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer of 0 to 4. When n3 is 1, n11 represents an integer of 0 to 6. When there are two or more R ３１ s, two or more R ３１ s may be the same or different. In the formula (A-22-2), Z １ 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. When there are two or more R ３２ s, two or more R ３２ s may be the same or different. When there are two or more R ３３ s, two or more R ３３ s may be the same or different. In the formula (A-22-3), Y １ and Y ２ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. When there are two or more R ３４ s, two or more R ３４ s may be the same or different. In the formula (A-22-4), Z ２ 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. R ３５ When there are two or more, two or more Rs ３５ may be the same or different. Rs ３６ When there are two or more, two or more Rs ３６ may be the same or different.) 7. The resist underlayer film-forming composition according to claim 1, wherein the mass ratio of the polymer (A) to the polymer (B) (polymer (A): polymer (B)) is 20:80 to 80:

20.

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

9. The resist underlayer film-forming composition according to claim 1, further comprising a crosslinking agent (D).

10. The resist underlayer film-forming composition according to claim 9, wherein the crosslinking agent (D) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

11. The resist underlayer film-forming composition according to claim 1, further comprising a curing catalyst (E).

12. The resist underlayer film-forming composition according to claim 1, which is used for EUV lithography.

13. The resist underlayer film-forming composition according to claim 1, which is used for forming an underlayer film of a metal-containing resist.

14. A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to any one of claims 1 to 13.

15. A laminate comprising a semiconductor substrate and the resist underlayer film according to claim 14.

16. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 13; and forming a resist film on the resist underlayer film.

17. A patterning method, comprising: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 13; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

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