Composition for resist underlayer film formation

Abstract

Provided are a composition for forming a resist underlayer film capable of forming a fine resist pattern with good sensitivity, a resist underlayer film using the composition for forming a resist underlayer film, a layered body, a method for manufacturing a semiconductor element, and a pattern forming method. A composition for forming a resist underlayer film, comprising a polymer (A) having, in a side chain, one or two or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds, and an aromatic hydrocarbon ring, and a solvent.

Description

Technical Field

[0001] This invention relates to compositions for forming a photoresist underlayer, photoresist underlayers, laminates, methods for manufacturing semiconductor devices, and methods for patterning. Background Technology

[0002] In the manufacture of semiconductor devices, photolithography using photoresist compositions has long been used for microfabrication. This microfabrication involves forming a thin film of photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern depicting the device, developing the film, and then using the resulting photoresist pattern as a protective film to etch the substrate, thereby forming a micro-unfolding pattern corresponding to the photoresist pattern on the substrate surface. In recent years, with the increasing integration of semiconductor devices, in addition to the commonly used i-rays (wavelength 365nm), KrF excimer lasers (wavelength 248nm), and ArF excimer lasers (wavelength 193nm), the practical application of EUV light (wavelength 13.5nm) or EB (electron beam) has been studied for the most advanced microfabrication. Along with this, poor photoresist pattern formation caused by influences from the semiconductor substrate has become a major problem. Therefore, to solve this problem, methods of setting a photoresist underlayer film between the photoresist and the semiconductor substrate have been extensively researched.

[0003] Patent Document 1 discloses a composition for forming a photolithographic underlayer film comprising a naphthalene ring having halogen atoms. Patent Document 2 discloses a halogenated antireflective film. Patent Document 3 discloses a composition for forming a resist underlayer film.

[0004] Existing technical documents

[0005] Patent documents

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

[0007] Patent Document 2: Japanese Patent Publication No. 2005-526270

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

[0009] The problem that the invention aims to solve

[0010] As required properties of the underlying resist film, examples include the ability to prevent mixing with the resist film formed on the upper layer (insoluble in resist solvent) and to form fine resist patterns.

[0011] The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a photoresist underlayer film capable of forming a photoresist underlayer film with good sensitivity, and a method for manufacturing a photoresist underlayer film, a stack, a semiconductor device, and a patterning method using the composition for forming a photoresist underlayer film.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, and completed the present invention with the following essential points.

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

[0015] [1] A composition for forming a resist underlayer film comprising a polymer (A) and a solvent, said polymer (A) having one or more polymerizable multiple bonds and an aromatic hydrocarbon ring selected from carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds and carbon-nitrogen triple bonds in its side chain.

[0016] [2] According to the composition for forming a resist underlayer film as described in [1], the polymer (A) has groups represented by the following formula (A).

[0017]

[0018] (In formula (A), L) 1 Indicates a single bond or linker. L 2 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 3 This refers to a monovalent group that has the aforementioned polymerizable multiple bonds. (This represents a bonding bond.)

[0019] [3] According to the composition for forming a resist underlayer film as described in [2], in the group shown in formula (A) above, the L above-mentioned L 2 It is represented by the following formula (b).

[0020]

[0021] (in formula (b), W 1 W 2 and W 3 Each can be independently a single bond, -O-, -C(=O)-O-, -OC(=O-, -OC(=O)-CH2-, -C(=O)-N(R')-, or -N(R')-C(=O)-. W 2 When the number is two or more, each W 2 They can be the same or different. R' represents an alkyl group with 1 to 6 carbon atoms.

[0022] Q is a single bond, or an alkylene group with 1 to 10 carbon atoms, or an alkenyl sub-chain with 2 to 10 carbon atoms. Some or all of the hydrogen atoms in the alkylene or alkenyl sub-chain may be replaced by halogen atoms.

[0023] L b It refers to a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linker formed by replacing one or more non-adjacent -CH2- atoms of an alkylene group having 1 to 12 carbon atoms with -O-, -S-, -C(=O)-O-, or OC(=O)-, wherein some or all of the hydrogen atoms of the alkylene group may be replaced by halogen atoms.

[0024] Q 1 It is a single bond, a phenylene, a naphthylene, or a divalent alicyclic hydrocarbon group with 5 to 8 carbon atoms, wherein some or all of the hydrogen atoms of the phenylene and naphthylene groups may be substituted by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkyl carbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms. Q 1 When the number of Q is two or more, each Q 1 They can be the same or different.

[0025] R b It is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group.

[0026] p can be 0, 1, 2, 3, or 4.

[0027] m is 0 or 1.

[0028] n1 can be 0, 1, 2 or 3.

[0029] a and b represents a bonding bond. a and L 1 Combine, b and L 3 (Combined.)

[0030] [4] According to the composition for forming a resist underlayer film as described in [3], the above-mentioned L 2 In the divalent group shown in formula (b) above, W 3 The combination with Q is any of the following combinations: W 3 It is a single key and Q is a single key, W 3 It is a single bond and Q is an alkylene group with 1 to 10 carbon atoms, and W 3 It is a single bond and Q is a sub-alkenyl group with 2 to 10 carbon atoms.

[0031] [5] According to the composition for forming a resist underlayer film as described in [3] or [4], the above-mentioned L 2 In the divalent group shown in formula (b) above, Q 1 With W 2 The combination is any of the following combinations: Q 1 It is a single key and W 2 Q is a single bond and n1 is 1. 1 It is a phenylene and W 2 It is -C(=O)-O-.

[0032] [6] The composition for forming a resist underlayer film according to any one of [3] to [5], wherein the above L 2 In the divalent group shown in formula (b) above, L b With W 1 The combination is any of the following combinations: L b It is a single key and W 1 For single bond, L b It is an alkylene group having 1 to 10 carbon atoms and W 1 For -OC(=O)-CH2-, and L b It is an alkylene group having 1 to 10 carbon atoms and W 1 It is -O-.

[0033] [7] The composition for forming a resist underlayer film according to any one of [2] to [6], wherein the group shown in formula (A) above, L 1 The connecting base has a structural part as shown in formula (t1) or formula (t2).

[0034]

[0035] (in the formula, 1 represents L in equation (A) 2 The bond on the opposite side of one side. 2 represents L in equation (A) 2 The bonding bond.

[0036] [8] The composition for forming a resist underlayer film according to any one of [2] to [7], wherein the group shown in formula (A) above, L 3 The monovalent group with polymerizable multiple bonds has the structural sites shown in formula (u1) or formula (u2).

[0037]

[0038] (in the formula, L in equation (A) 2 The bonding bond.

[0039] [9] According to the composition for forming a resist underlayer film as described in [1], the polymer (A) has the structural unit shown in the following formula (1).

[0040]

[0041] (In equation (1), R) 1 Indicates an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. L 11 Indicates a single bond or linker. L 12 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 13 (This refers to a monovalent group possessing the aforementioned polymerizable multiple bonds.)

[0042]

[10] According to the composition for forming a resist underlayer film as described in [9], in the structural unit shown in formula (1) above, the above L 11 The connection base is represented by the following formula (L1-1) or the following formula (L1-2).

[0043]

[0044] (in the formula, 1 indicates the combination with R in equation (1) 1 The carbon atoms are bonded together by a bonding bond. 2 represents L in equation (1) 12 The bonding bond.

[0045]

[11] According to the composition for forming a resist underlayer film as described in [1], the polymer (A) has the structural unit shown in the following formula (2).

[0046]

[0047] (In equation (2), R) a Represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. Ar represents a benzene ring, naphthalene ring, or anthracene ring. L X This indicates a single bond or a divalent group that may have substituents. L 21 Indicates a single bond or linker. L 22 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 23 This represents a monovalent group with the aforementioned polymerizable multiple bonds. n1 is an integer from 0 to 3.

[0048]

[12] According to the composition for forming a resist underlayer film as described in

[11] , in the structural unit shown in the above formula (2), the above L 21 The connection base is represented by the following equation (L1-12).

[0049]

[0050] (in the formula, 1 represents the bonding bond that binds to Ar in equation (2). 2 represents L in equation (1) 22 The bonding bond.

[0051]

[13] According to the composition for forming a resist underlayer film as described in [1], the polymer (A) has the structural unit shown in the following formula (3).

[0052]

[0053] (In equation (3), L) 31 Indicates a single bond or linker. L 32 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 33 (This refers to a monovalent group possessing the aforementioned polymerizable multiple bonds.)

[0054]

[14] According to the composition for forming a resist underlayer film as described in

[13] , in the structural unit shown in formula (3) above, the above L 31 The connection base is represented by the following equation (L1-13).

[0055]

[0056] (in the formula, 1 represents the bonding bond with the alicyclic hydrocarbon in formula (3). 2 represents L in equation (3) 32 The bonding bond.

[0057]

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

[15] further comprises a crosslinking agent.

[0058]

[16] A resist underlayer film, which is a cured product of the resist underlayer film forming composition described in any one of [1] to

[15] .

[0059]

[17] A laminated body comprising: Semiconductor substrates, and

[16] The lower layer film of the resist.

[0060]

[18] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a semiconductor substrate using any one of [1] to

[15] 's composition for forming a photoresist underlayer film; and The process of forming a resist film on the lower resist film mentioned above.

[0061]

[19] A pattern forming method comprising the following steps: The process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film according to any one of [1] to

[15] ; The process of forming a resist film on the aforementioned lower resist film; The process of irradiating the above-mentioned resist film with light or an electron beam, and then developing the above-mentioned resist film to obtain a resist pattern; and The process of using the above-mentioned resist pattern as a mask to etch the above-mentioned resist underlayer film.

[0062] The effects of the invention

[0063] According to the present invention, a composition for forming a photoresist underlayer film capable of forming a photoresist underlayer film with good sensitivity can be provided, as well as a method for manufacturing a photoresist underlayer film, a stack, a semiconductor device, and a patterning method using the composition for forming a photoresist underlayer film. Attached Figure Description

[0064] Figure 1 This is a photograph showing an observation of the resist pattern formed in Example 1. Detailed Implementation

[0065] (Composition for forming the lower layer film of the resist)

[0066] The composition for forming the resist underlayer film of the present invention comprises a polymer (A) and a solvent.

[0067] The composition for forming the lower layer film of the resist may include a crosslinking agent, a curing catalyst, a thermal free radical polymerization initiator, etc.

[0068] A resist pattern with good sensitivity can be formed on a resist underlayer film formed by a composition comprising a polymer (A) and a solvent.

[0069] <Polymer (A)>

[0070] Polymer (A) has polymerizable multiple bonds and an aromatic hydrocarbon ring in its side chain. The polymerizable multiple bonds and the aromatic hydrocarbon ring preferably exist within the same side chain.

[0071] The polymerizable multiple bond is one or more polymerizable multiple bonds selected from carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0072] Polymer (A) is an organic polymer.

[0073] Polymer (A) can be a homopolymer or a copolymer.

[0074] Polymer (A) has, for example, (meth)acryloyl, vinylaryl (e.g., styrene), vinyloxy, allyl, etc. as groups with the above-mentioned polymerizable multiple bonds in its side chain.

[0075] The polymer (A) preferably has groups represented by the following formula (A).

[0076]

[0077] (In formula (A), L) 1 Indicates a single bond or linker. L 2 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 3 This refers to a monovalent group that has the aforementioned polymerizable multiple bonds. (This represents a bonding bond.)

[0078] In the group shown in formula (A), L 2 The preferred expression is represented by the following formula (b).

[0079]

[0080] (in formula (b), W 1 W 2 and W 3 Each can be independently a single bond, -O-, -C(=O)-O-, -OC(=O-, -OC(=O)-CH2-, -C(=O)-N(R')-, or -N(R')-C(=O)-. W 2 When the number is two or more, each W 2 They can be the same or different. R' represents an alkyl group with 1 to 6 carbon atoms.

[0081] Q is a single bond, or an alkylene group with 1 to 10 carbon atoms, or an alkenyl sub-chain with 2 to 10 carbon atoms. Some or all of the hydrogen atoms of the alkylene group or alkenyl sub-chain may be replaced by halogen atoms.

[0082] L b It refers to a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linker formed by replacing one or more non-adjacent -CH2- atoms of an alkylene group having 1 to 12 carbon atoms with -O-, -S-, -C(=O)-O-, or OC(=O)-, wherein some or all of the hydrogen atoms of the alkylene group may be replaced by halogen atoms.

[0083] Q 1It is a single bond, a phenylene, a naphthylene, or a divalent alicyclic hydrocarbon group with 5 to 8 carbon atoms, wherein some or all of the hydrogen atoms of the phenylene and naphthylene groups may be substituted by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkyl carbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms. Q 1 When the number of Q is two or more, each Q 1 They can be the same or different.

[0084] R b It is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group.

[0085] p can be 0, 1, 2, 3, or 4.

[0086] m is 0 or 1.

[0087] n1 can be 0, 1, 2 or 3.

[0088] a and b represents a bonding bond. a and L 1 Combine, b and L 3 (Combined.)

[0089] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl 1,2-Dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-Ethyl-cyclopropyl, 2-Ethyl-cyclopropyl, n-Hexyl, 1-Methyl-n-pentyl, 2-Methyl-n-pentyl, 3-Methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl -n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl Cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, cycloheptyl, norbornyl, n-octyl, cyclooctyl, n-nonyl, isobornyl, tricyclononyl, n-decyl, adamantyl, tricyclodecyl, etc. Among these, methyl is preferred.

[0090] Subchain alkenyl groups are linear or branched and may contain at least one double bond in the chain. Examples of subchain alkenyl groups with 2 to 10 carbon atoms include vinylene, 1-propenylene, 2-propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, 1-hexenylene, and 2-hexenylene.

[0091] In formula (A) L 1 In the case of a linker, there is no particular limitation on the number of carbon atoms that serve as the linker, and examples include 1 to 10.

[0092] L 1In the case of a linker, examples of linkers include linkers having a structure obtained by reacting an epoxy group with a nucleated functional group.

[0093] Here, when referring to nuclear functional groups, examples include one or more selected from carboxyl, hydroxyl, amino, and thiol groups. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0094] As L 1 The connecting base preferably has a structural part as shown in formula (t1) or formula (t2).

[0095]

[0096] (in the formula, 1 represents L in equation (A) 2 The bond on the opposite side of one side. 2 represents L in equation (A) 2 The bonding bond.

[0097] As L 1 Examples of such connections include the following linkers (L1-1) to (L1-11).

[0098]

[0099] (in the formula, 1 represents L in equation (A) 2 The bond on the opposite side of one side. 2 represents L in equation (A) 2 The bonding bond.

[0100] As L 2 It is a divalent group having an aromatic hydrocarbon ring, for example, preferably the divalent group shown in formula (b) above.

[0101] As a preferred embodiment of the divalent group shown in formula (b), the following examples can be cited.

[0102] In the divalent group shown in formula (b), as W 3 The combination with Q is preferably any of the following combinations: W 3 It is a single key and Q is a single key, W 3 It is a single bond and Q is an alkylene group with 1 to 10 carbon atoms, and W 3 It is a single bond and Q is a sub-alkenyl group with 2 to 10 carbon atoms.

[0103] In the divalent group shown in formula (b), as Q1 With W 2 The combination of Q is preferred, preferably any one of the following combinations: 1 It is a single key and W 2 Q is a single bond and n1 is 1. 1 It is a phenylene and W 2 It is -C(=O)-O-.

[0104] In the divalent group shown in formula (b), as L b With W 1 The combination of L is preferred, preferably any one of the following combinations: b It is a single key and W 1 For single bond, L b It is an alkylene group having 1 to 10 carbon atoms and W 1 For -OC(=O)-CH2-, and L b It is an alkylene group having 1 to 10 carbon atoms and W 1 It is -O-.

[0105] As L 2 Examples of such divalent groups include (L2-1) to (L2-5).

[0106]

[0107] (in the formula, a represents L in equation (A) 1 The bonding bonds of the combination, b represents L in equation (A) 3 The bonding bond.

[0108] L 3 It is a monovalent group with polymerizable multiple bonds. The monovalent group can also be the polymerizable multiple bond itself.

[0109] There is no particular restriction on the number of carbon atoms in the monovalent group; for example, it can be 1 to 20 or 1 to 10.

[0110] As L 3 The monovalent group having polymerizable multiple bonds preferably has the structural sites shown in formula (u1) or formula (u2).

[0111]

[0112] (in the formula, L in equation (A) 2 The bonding bond.

[0113] As L 3Examples of such examples include the following monovalent groups (L3-1)~(L3-81).

[0114]

[0115] (in the formula, (This represents a bonding bond.)

[0116] Polymer (A) having the groups shown in formula (A) can be obtained, for example, by reacting a resin containing epoxy groups with a resin containing nucleated functional groups.

[0117] As a nuclear functional group, examples include one or more selected from carboxyl, hydroxyl, amino, and thiol groups. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0118] For example, if an epoxy group reacts with a carboxyl group, the reaction is as follows, forming the following structure (S1).

[0119]

[0120] (in the formula, (This represents a bonding bond.)

[0121] As a preferred embodiment of the polymer (A) involved in the present invention, examples include the polymers described in the first to third embodiments below.

[0122] <<Implementation Plan 1>>

[0123] As an example of polymer (A) in the first embodiment, a polymer having structural units as shown in the following formula (1) can be cited.

[0124]

[0125] (In equation (1), R) 1 Indicates an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. L 11 Indicates a single bond or linker. L 12 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 13 (This refers to a monovalent group possessing the aforementioned polymerizable multiple bonds.)

[0126] L 11 L in equation (A) 1 The same meaning.

[0127] L 12 L in equation (A) 2 The same meaning.

[0128] L 13 L in equation (A) 3 The same meaning.

[0129] In this invention, in formula (1), L 11 The linker is preferably a group represented by the following formula (L1-1) or the following formula (L1-2).

[0130]

[0131] (in the formula, 1 indicates the combination with R in equation (1) 1 The carbon atoms are bonded together by a bonding bond. 2 represents L in equation (1) 12 The bonding bond.

[0132] The polymer (A) of the first embodiment can be obtained, for example, by reacting a compound (C1) having polymerizable multiple bonds, an aromatic hydrocarbon ring, and a carboxyl group with a glycidyl methacrylate-based polymer (E1) as described below. The glycidyl methacrylate-based polymer can be a homopolymer or a copolymer. Examples of copolymers include, for instance, a copolymer of glycidyl methacrylate and 2-hydroxyethyl methacrylate, and a copolymer of glycidyl methacrylate and 2-hydroxypropyl methacrylate.

[0133]

[0134] (where R is in the formula) 1 R in equation (1) 1 They have the same meaning. L 2 With L in equation (1) 12 They have the same meaning. L 3 L in equation (1) 13 The meaning is the same.

[0135] The reaction can be performed, for example, by tetrabutyl bromide. The process is carried out in the presence of a catalyst.

[0136] <<Second Implementation Plan>>

[0137] As an example of polymer (A) in the second embodiment, a polymer having structural units as shown in the following formula (2) can be cited.

[0138]

[0139] (In equation (2), R) a Represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. Ar represents a benzene ring, naphthalene ring, or anthracene ring. L X This indicates a single bond or a divalent group that may have substituents. L 21 Indicates a single bond or linker. L 22 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 23 This represents a monovalent group with the aforementioned polymerizable multiple bonds. n1 is an integer from 0 to 3.

[0140] L 21 L in equation (A) 1 The same meaning.

[0141] L 22 L in equation (A) 2 The same meaning.

[0142] L 23 L in equation (A) 3 The same meaning.

[0143] In this invention, in formula (2), L 21 The linker is preferably a group represented by the following formula (L1-12).

[0144]

[0145] (in the formula, 1 represents the bonding bond that binds to Ar in equation (2). 2 represents L in equation (1) 22 The bonding bond.

[0146] L X The divalent group represents, for example, an alkylene group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 25 carbon atoms, or a group obtained by combining two or more of these groups.

[0147] L X The alkylene group can be any type of alkylene group that is linear, branched, or cyclic.

[0148] As L X Aromatic hydrocarbon groups can be categorized as monocyclic or fused-ring aromatic hydrocarbon groups, or as linking rings attached to these aromatic hydrocarbon groups.

[0149] As LX Substituents that can replace the divalent group include groups containing (meth)acryloyloxy and alkoxy groups.

[0150] The polymer (A) of the second embodiment can be obtained by reacting a polymer having the structural unit shown in the following formula (2-1') with a compound having polymerizable multiple bonds, an aromatic hydrocarbon ring and a carboxyl group.

[0151]

[0152] (In equation (2-1'), Ar and R) a n1, L X respectively with Ar and R in equation (2) a n1, L X They have the same meaning. T 1 This indicates a single bond, or an alkylene group with 1 to 10 carbon atoms, which may be interrupted by an ether, ester, or amide bond. E represents a group containing an epoxy group.

[0153] The polymer (A) of the second embodiment can be obtained, for example, by reacting a compound (C1) having polymerizable multiple bonds, an aromatic hydrocarbon ring and a carboxyl group with the following polymer (E2) having an epoxy group.

[0154]

[0155] (where L) 2 L in equation (2) 22 They have the same meaning. L 3 L in equation (2) 23 The meaning is the same.

[0156] As a polymer having the structural unit shown in formula (2-1'), substances having the following structural units can be cited.

[0157]

[0158] <<Implementation Plan 3>>

[0159] As an example of polymer (A) in the third embodiment, a polymer having structural units as shown in the following formula (3) can be cited.

[0160]

[0161] (In equation (3), L) 31 Indicates a single bond or linker. L 32 This indicates a divalent group having the aforementioned aromatic hydrocarbon ring. L 33 (This refers to a monovalent group possessing the aforementioned polymerizable multiple bonds.)

[0162] L 31 L in equation (A) 1 The same meaning.

[0163] L 32 L in equation (A) 2 The same meaning.

[0164] L 33 L in equation (A) 3 The same meaning.

[0165] In this invention, in formula (3), L 31 The linker is preferably a group represented by the following formula (L1-13).

[0166]

[0167] (in the formula, 1 represents the bonding bond with the alicyclic hydrocarbon in formula (3). 2 represents L in equation (3) 32 The bonding bond.

[0168] The polymer (A) of the third embodiment can be obtained by reacting a polymer having the structural unit shown in the following formula (3-1') with a compound having polymerizable multiple bonds, an aromatic hydrocarbon ring and a carboxyl group.

[0169]

[0170] (In formula (3-1'), E is a group with an epoxy group.)

[0171] The polymer (A) of the third embodiment can be obtained, for example, by reacting a compound (C1) having polymerizable multiple bonds, an aromatic hydrocarbon ring and a carboxyl group with the following polymer (E3) having an epoxy group.

[0172]

[0173] (where L) 2 L in equation (3) 32 They have the same meaning. L 3 L in equation (3) 33 The meaning is the same.

[0174] As a polymer having the structural unit shown in formula (3-1'), examples of substances having the following structural units can be cited.

[0175]

[0176] As a preferred embodiment of polymer (A), examples include polymers having the following structural units.

[0177]

[0178] Polymer (A) may also have structural units other than those shown in formula (1). Examples of such structural units include those shown in formula (4), formula (5), and formula (6).

[0179]

[0180] (In equation (4), R) 2 L represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 30 It represents a monovalent group with 1 to 20 carbon atoms.

[0181] In equation (5), R 2 Indicates a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; Ar indicates a benzene ring or a naphthalene ring; L 40 This indicates a hydroxyl, cyano, nitro, or amino group (-NH2). L 50 This represents a halogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. m1 represents an integer from 0 to 3. m2 represents an integer from 0 to 5. The sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L... 40 They can be the same or different. When m² is 2~5, multiple L... 50 They can be the same or different.

[0182] In equation (6), R 2 L represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 60 It represents a monovalent organogroup selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms, wherein at least one hydrogen atom of the alkyl group and the aryl group can be replaced by a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

[0183] L in equation (4) 30 The monovalent group having 1 to 20 carbon atoms represents, for example, a monovalent organogroup selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms, wherein at least one hydrogen atom of the alkyl group and the aryl group can be replaced by a hydroxyl group. In addition, oxygen atoms can be inserted between carbon atoms of the alkyl group.

[0184] Additionally, as L 30 The monovalent group having 1 to 20 carbon atoms can be exemplified by, for example, the group shown in the following formula (4-1).

[0185]

[0186] (In equation (4-1), L) 3a This refers to alkyl groups with 1 to 6 carbon atoms that can be substituted, or aromatic hydrocarbon groups that can be substituted.

[0187] As L 3a Aromatic hydrocarbon groups in the form of phenyl or naphthyl groups can be cited as examples.

[0188] As L 3a The substituents can be substituted in alkyl groups having 1 to 6 carbon atoms, such as halogen atoms and hydroxyl groups. There can be one or more substituents. When there are multiple substituents, the substituents can be the same or different.

[0189] As L 3a Substituents in substituted aromatic hydrocarbon groups can include, for example, halogen atoms, hydroxyl groups, and alkyl groups with 1 to 3 carbon atoms that can be replaced by halogen atoms. There can be one or more substituents. When there are multiple substituents, they can be the same or different.

[0190] R 2 Alkyl groups with 1 to 10 carbon atoms, and L 30 and L 60 Specific examples of alkyl groups with 1 to 10 carbon atoms are shown above.

[0191] As L 50 Halogen atoms in halogen atoms can be exemplified by fluorine, chlorine, bromine, and iodine atoms.

[0192] As L 50 Alkyl groups having 1 to 6 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, etc.

[0193] As L 50 Alkoxy groups with 1 to 6 carbon atoms can be exemplified by, for example, methoxy, ethoxy, propoxy, and butoxy.

[0194] m1 represents an integer from 0 to 3, which can be 0, 1, 2, or 3.

[0195] m2 represents an integer from 0 to 5, which can be 0, 1, 2, 3, 4, or 5.

[0196] As L 30 and L 60Examples of aryl groups with 6 to 40 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0197] As L 60 Alkoxy groups with 1 to 6 carbon atoms can be exemplified by, for example, methoxy, ethoxy, propoxy, and butoxy.

[0198] The proportion of the structural units represented by at least any one of formulas (1) to (3) in polymer (A) is not particularly limited. For example, the molar ratio of any structural unit represented by formulas (1) to (3) relative to all structural units of polymer (A) can be 20 mol% to 100 mol%, or more than 20 mol% and less than 100 mol%.

[0199] There is no particular limitation on the proportion of the structural units shown in formula (4) in polymer (A). For example, the molar ratio of the structural units shown in formula (4) relative to all structural units of polymer (A) can be 0 mol% to 80 mol%, or it can be more than 0 mol% and less than 80 mol%.

[0200] Polymer (A) may contain structural units other than those shown in any of formulas (1) to (3) and formula (4). In this case, the molar percentage of the other structural units in all structural units of polymer (A) is, for example, more than 0 mol% and less than 20 mol%.

[0201] Polymer (A) is, for example, not a polysiloxane.

[0202] Polymer (A) is, for example, a hydrolytic condensate of a non-hydrolytic silane.

[0203] Polymer (A) is, for example, not a product of the reaction of tetracarboxylic dianhydride with a diepoxide having two epoxide groups.

[0204] Polymer (A) is, for example, a reaction product that is not a tetracarboxylic dianhydride, a diepoxide compound having two epoxy groups, or a monohydroxy compound having one hydroxyl group.

[0205] Polymer (A), for example, does not have an isocyanuric acid backbone containing an alkenyl group. Examples of alkenyl groups include, for example, alkenyl groups with 3 to 6 carbon atoms. Examples of alkenyl groups with 3 to 6 carbon atoms include, for example, allyl groups.

[0206] The molecular weight of polymer (A) is not particularly limited.

[0207] The lower limit of the weight-average molecular weight of polymer (A) is, for example, 500, 1,000, 2,000, or 3,000.

[0208] The upper limit of the weight-average molecular weight of polymer (A) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0209] Solvent

[0210] As a solvent, there are no particular restrictions; it can be water or an organic solvent.

[0211] Examples of organic solvents include, for example, monoalkylene glycol monoalkyl ethers and monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers.

[0212] Examples of alkylene groups that are monoalkylene glycol ethers include those with 2 to 4 carbon atoms.

[0213] Examples of alkyl groups that are monoalkylene glycol ethers include alkyl groups having 1 to 4 carbon atoms.

[0214] Examples of alkylene glycol monoalkyl ethers with 3 to 8 carbon atoms are given.

[0215] Examples of alkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0216] Examples of alkylene derivatives that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene derivatives with 2 to 4 carbon atoms.

[0217] Examples of alkyl groups that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms.

[0218] Monocarboxylic acids that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids with 2 to 4 carbon atoms.

[0219] Examples of saturated monocarboxylic acids with 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0220] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, 5 to 10 carbon atoms.

[0221] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, methyl cellolytic acetate, ethyl cellolytic acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0222] 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 ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0223] Among these solvents, monoalkylene glycol monoalkyl ethers and monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers are preferred.

[0224] These solvents can be used alone or in combination of two or more.

[0225] The mass ratio of organic solvent in the solvent is not particularly limited, but is preferably 50% to 100% by mass.

[0226] The content of the solvent in the composition for forming the lower layer of the resist film is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0227] Crosslinking agent

[0228] There are no particular restrictions on its use as a crosslinking agent.

[0229] The crosslinking agent has a different structure from polymer (A).

[0230] As crosslinking agents, amino plastic crosslinking agents and phenolic plastic crosslinking agents are preferred.

[0231] Amino plastic crosslinking agents are addition condensations of amino compounds such as melamine and melamine with formaldehyde.

[0232] Phenolic plastic crosslinking agents are addition condensation compounds of compounds with phenolic hydroxyl groups and formaldehyde.

[0233] Examples of crosslinking agents include compounds having two or more of the following structures.

[0234]

[0235] (In the structure, R) 101 It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. (This represents a bonding bond.)

[0236] Bonding bonds include, for example, bonds with nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0237] As R 101 Preferably, it contains hydrogen atoms, methyl, ethyl or groups represented by the following structures.

[0238]

[0239] (In the structure, R) 102 It represents a hydrogen atom, a methyl group, or an ethyl group. (This represents a bonding bond.)

[0240] Preferred crosslinking agents include melamine compounds, melamine diamine compounds, glycourea compounds, urea compounds, and compounds with phenolic hydroxyl groups. They can be used alone or in combination of two or more.

[0241] Examples of melamine compounds include hexahydroxymethyl melamine, hexamethoxymethyl melamine, compounds obtained by methoxymethylating 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, and mixtures thereof; hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds obtained by acyloxymethylating 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, and mixtures thereof.

[0242] Examples of melamine compounds include tetrahydroxymethyl melamine, tetramethoxymethyl melamine, compounds obtained by methoxymethylating one to four hydroxymethyl groups of tetrahydroxymethyl melamine, or mixtures thereof; tetramethoxyethyl melamine, tetraacyloxymelamine, compounds obtained by acyloxymethylating one to four hydroxymethyl groups of tetrahydroxymethyl melamine, or mixtures thereof.

[0243] Examples of glycourea compounds include tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, and mixtures thereof, as well as compounds obtained by acylmethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea.

[0244] Alternatively, the glycourea compound may be, for example, a glycourea derivative as shown in formula (1E).

[0245]

[0246] (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.)

[0247] Examples of compounds shown in formula (1E) to (1E-6) below are glycourea derivatives shown in formula (1E) above.

[0248]

[0249] The glycourea derivative shown in formula (1E) can be obtained by reacting, for example, the glycourea derivative shown in formula (2E) below with at least one compound shown in formula (3d) below.

[0250]

[0251] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group with 1 to 4 carbon atoms.)

[0252] (In formula (3d), R1 represents methyl or ethyl.)

[0253] Examples of compounds shown in formula (2E) to (2E-4) below are examples of glycourea derivatives. Furthermore, examples of compounds shown in formula (3d) below are examples of compounds shown in formula (3d-1) and (3d-2).

[0254]

[0255] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds or mixtures thereof obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetrahydroxymethylurea, and tetramethoxyethylurea.

[0256] Examples of compounds having phenolic hydroxyl groups include compounds represented by formula (G-1) or formula (G-2) below.

[0257]

[0258] In equations (G-1) and (G-2), Q 1 Organic groups that represent single bonds or m1 valence.

[0259] R 1 and R 4 Each represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.

[0260] R 2 and R 5 Each represents a hydrogen atom or a methyl group.

[0261] R 3 and R 6 Each represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 40 carbon atoms.

[0262] n1 represents an integer where 1 ≤ n1 ≤ 3, n2 represents an integer where 2 ≤ n2 ≤ 5, n3 represents an integer where 0 ≤ n3 ≤ 3, n4 represents an integer where 0 ≤ n4 ≤ 3, and n1, n2, n3, and n4 represent integers where 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0263] n5 represents an integer where 1 ≤ n5 ≤ 3, n6 represents an integer where 1 ≤ n6 ≤ 4, n7 represents an integer where 0 ≤ n7 ≤ 3, n8 represents an integer where 0 ≤ n8 ≤ 3, and n5, n6, n7, and n8 represent integers where 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0264] m1 represents an integer from 2 to 10.

[0265] In addition, compounds having phenolic hydroxyl groups can be exemplified by compounds shown in formula (G-3) or formula (G-4) below.

[0266] The compounds shown in formula (G-1) or (G-2) can also be obtained by reacting the compounds shown in formula (G-3) or (G-4) below with ether compounds containing hydroxyl groups or alcohols having 2 to 10 carbon atoms.

[0267]

[0268] In equations (G-3) and (G-4), Q 2 Organic groups that represent single bonds or m2 valence.

[0269] R 8 R 9 R 11 and R 12 Each represents a hydrogen atom or a methyl group.

[0270] R 7 and R 10 Each represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 40 carbon atoms.

[0271] n9 represents an integer where 1 ≤ n9 ≤ 3, and n 10 It means 2≤n 10 Integers ≤ 5, n 11 It means 0≤n 11 Integers ≤3, n 12 It means 0≤n 12 Integers ≤ 3, and n = 9, n 10 n 11 n 12This means 3 ≤ (n9 + n) 10 +n 11 +n 12 Integers ≤ 6.

[0272] n 13 It means 1≤n 13 Integers ≤3, n 14 It means 1≤n 14 Integers ≤ 4, n 15 It means 0≤n 15 Integers ≤3, n 16 It means 0≤n 16 Integers ≤ 3, and n 13 n 14 n 15 n 16 It means 2≤(n) 13 +n 14 +n 15 +n 16 Integers ≤ 5.

[0273] m2 represents an integer from 2 to 10.

[0274] As Q 2 Organic groups with an m2 valence can be exemplified by organic groups with an m2 valence having 1 to 4 carbon atoms.

[0275] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0276]

[0277] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0278]

[0279] The above-mentioned compounds can be obtained as products manufactured by Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, Asahi Organic Materials Co., Ltd.'s trade name TMOM-BP can be cited as an example of such a product.

[0280] Among them, glycourea compounds are preferred, specifically tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds or mixtures thereof obtained by methoxymethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, compounds or mixtures thereof obtained by acylmethylation of 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea, with tetramethoxymethylglycourea being the most preferred.

[0281] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 500 or less.

[0282] The content of the crosslinking agent in the composition for forming the lower layer of the resist film is not particularly limited, and is, for example, 1% to 50% by mass relative to the polymer (A), preferably 5% to 40% by mass.

[0283] <Catalyst Solidification>

[0284] As a curing catalyst included as an optional component in the composition for forming the lower layer film of the resist, both thermal acid-generating agents and photo-acid-generating agents can be used, with thermal acid-generating agents being preferred.

[0285] Examples of heat-generating acid agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pyridine. p-Toluenesulfonate (p-Toluenesulfonic acid pyridine) ), Pyridine phenolsulfonate pyridine p-hydroxybenzenesulfonic acid (pyridine p-phenolsulfonate) (salt), pyridine trifluoromethanesulfonate Sulfonic acid compounds and carboxylic acid compounds, such as salicylic acid, camphor sulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzene disulfonic 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.

[0286] Examples of photoacid-producing agents include: Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0287] As Salt compounds, for example, diphenyliodine Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, and sulfonate compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0288] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0289] Examples of disulfonyl diazonium compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0290] A single solidification catalyst may be used, or two or more may be used in combination.

[0291] When using a curing catalyst, the content of the curing catalyst relative to the crosslinking agent is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0292] <Other Ingredients>

[0293] In the composition for forming the lower layer of the resist film, a surfactant can be added to further improve the coating properties on uneven surfaces in order to prevent pinholes, streaks, etc.

[0294] Examples of surfactants include, for example, linear or branched alkylbenzene sulfonic acids (e.g., dodecylbenzene sulfonic acid), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oil-based ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitol monolaurate, sorbitol monopalmitate, and sorbitol monolaurate. Nonionic surfactants including sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters; EF301, EF303, EF352 ((Industry Co., Ltd.) (Product name) F171, F173, R-30 (manufactured by DIC Corporation, trade name) FC430, FC431 (Company name, product name) AG710 Fluorinated surfactants such as S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation, trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0295] The amount of these surfactants mixed in is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid components of the composition for forming the lower layer of the resist film.

[0296] These surfactants can be added individually or in combination of two or more.

[0297] The composition for forming the lower layer of the resist film may contain a polymerization inhibitor (free radical scavenger) as needed. Examples of polymerization inhibitors include, for example, 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, 4-methoxy-1-naphthol, etc.

[0298] The content of the polymerization inhibitor in the composition for forming the lower layer film of the resist is not particularly limited, but it is preferably less than 1% by mass relative to the solid content.

[0299] The solid component contained in the resist lower film forming composition of the present invention, that is, the component after removing the solvent, is, for example, 0.01% to 10% by mass.

[0300] The composition for forming the resist underlayer is suitable for use in EUV lithography.

[0301] The composition for forming a resist underlayer film is suitable for forming an underlayer film of a metal-containing resist.

[0302] (Resist underlayer film)

[0303] The resist underlayer film of the present invention is a cured product of the aforementioned resist underlayer film forming composition.

[0304] The resist underlayer film can be manufactured, for example, by coating the aforementioned resist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0305] Examples of semiconductor substrates that can be used to form a composition for coating a resist underlayer include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0306] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (boro-phosphorus silicon glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0307] On such a semiconductor substrate, the resist underlayer film formation composition of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, it is baked using a heating means such as a heating plate to form the 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 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0308] The thickness of the underlying resist film is, for example, 0.001 μm (1 nm) ~ 10 μm, 0.002 μm (2 nm) ~ 1 μm, 0.005 μm (5 nm) ~ 0.5 μm (500 nm), 0.001 μm (1 nm) ~ 0.05 μm (50 nm), 0.002 μm (2 nm) ~ 0.05 μm (50 nm), 0.003 μm (3 nm) ~ 0.05 μm (50 nm), 0.004 μm (4 nm) ~ 0.05 μm (50 nm), 0.005 μm (5 nm) ~ 0.05 μm (500 nm). 0nm), 0.003μm (3nm)~0.03μm (30nm), 0.003μm (3nm)~0.02μm (20nm), 0.005μm (5nm)~0.02μm (20nm), 0.005μm (5nm)~0.02μm (20nm), 0.003μm (3nm)~0.01μm (10nm), 0.005μm (5nm)~0.01μm (10nm), 0.003μm (3nm)~0.006μm (6nm), or 0.005μm (5nm).

[0309] The method for determining the thickness of the resist underlayer film in this specification is as follows.

[0310] • Measuring device name: Elliptic film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0311] • SWE (Single Wavelength Ellipsometry) Mode

[0312] • Arithmetic mean of 8 points (e.g., measured at 1cm intervals along the X-axis of the wafer).

[0313] (Laminated structure)

[0314] The stack of the present invention comprises a semiconductor substrate and a photoresist underlayer film of the present invention.

[0315] Examples of semiconductor substrates include those mentioned above.

[0316] The photoresist underlayer is, for example, disposed on a semiconductor substrate.

[0317] (Semiconductor device manufacturing methods, patterning methods)

[0318] The method for manufacturing the semiconductor device of the present invention includes at least the following steps.

[0319] • The process of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition of the present invention, and

[0320] • The process of forming a resist film on the resist underlayer film.

[0321] The pattern forming method of the present invention includes at least the following steps.

[0322] • A process for forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention; • The process of forming a resist film on the underlying resist film; • The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern; and • A process of etching an underlying resist film by using a resist pattern as a mask.

[0323] Typically, a resist layer is formed on the lower resist film.

[0324] The thickness of the resist layer 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.

[0325] As a resist film formed on a resist underlayer by known methods (e.g., coating and firing of the resist composition), there are no particular limitations as long as it responds to the light or electron beam (EB) used for irradiation. Both negative and positive photoresists can be used.

[0326] It should be noted that, in this specification, the EB-responsive resist is also referred to as a photoresist.

[0327] As photoresists, there are positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonium sulfonate; chemically amplified photoresists composed of binders and photoacid generators having groups that increase the alkali dissolution rate of photoresists through acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the alkali dissolution rate of photoresists through acid decomposition; alkali-soluble binders and photoacid generators; chemically amplified photoresists composed of binders having groups that increase the alkali dissolution rate of photoresists through acid decomposition; low-molecular-weight compounds that increase the alkali dissolution rate of photoresists through acid decomposition; and photoacid generators; as well as photoresists containing metal elements. For example, JSR Corporation's trade name V146G can be cited. The company produces products under the brand name APEX-E, Sumitomo Chemical Co., Ltd. produces products under the brand name PAR710, and Shin-Etsu Chemical Co., Ltd. produces products under the brand names AR2772 and SEPR430. Additionally, examples include fluorinated polymer photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0328] Alternatively, you can use WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, W O2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japan Special opening 2016-035567, Japanese special opening 2016-035565, Japanese special opening 2019-101417, Japanese special opening 2019-117373, Japan Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019-06 1217. Japan Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 201 The so-called resist compositions, such as resist compositions, radiation-sensitive resin compositions, and compositions for high-resolution patterning based on organometallic solutions, as described in 1-043749, Japanese Patent Application Publication No. 2010-181857, Japanese Patent Application Publication No. 2010-128369, WO2018 / 031896, Japanese Patent Application Publication No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Publication No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Publication No. 2016-29498, and Japanese Patent Application Publication No. 2011-253185, are metal-containing resist compositions, but are not limited to these.

[0329] Examples of resist compositions include the following.

[0330] An active light-sensitive or radiation-sensitive resin composition comprising resin A and a compound represented by the following general formula (121), wherein resin A has repeating units having acid-degradable groups that are protected by protecting groups that are deactivated by acid.

[0331]

[0332] In general formula (121), m represents an integer from 1 to 6.

[0333] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0334] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0335] L2 indicates that it can have alkylene groups or single bonds that have substituents.

[0336] W1 represents a cyclic organic group that can have substituents.

[0337] M + It represents a cation.

[0338] A metal-containing film-forming composition for 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 the 3rd to 7th periods of Groups 3 to 15 of the periodic table.

[0339] A radiation-sensitive resin composition comprising a polymer and an acid-generating agent, said polymer having a first structural unit as shown in formula (31) and a second structural unit as shown in formula (32) and containing an acid-dissociating group.

[0340]

[0341] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon with 6 to 20 carbon atoms. R 1 It can be a hydroxyl group, a thiol group, or a monovalent organic group with 1 to 20 carbon atoms. n is an integer from 0 to 11. When n is 2 or more, multiple R... 1 They can be the same or different. R 2 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 It is a monovalent group containing 1 to 20 carbon atoms, including the acid-dissociating group mentioned above. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0342] An anti-corrosion composition comprising a resin (A1) and an acid-generating agent, wherein the resin (A1) comprises structural units having a cyclic carbonate structure, structural units represented by the following formula, and structural units having an acid-instantaneous group.

[0343]

[0344] [In the formula, R 2 X represents an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that can have halogen atoms. 1 Indicates a single bond, -CO-O- or -CO-NR 4 - , R represents the bond with -Ar. 4 [Ar represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have one or more groups selected from hydroxyl and carboxyl groups.] Examples of resist films include the following.

[0345] A photoresist film comprising a base resin containing repeating units as shown in formula (a1) and / or repeating units as shown in formula (a2), and repeating units of acid bonded to the polymer backbone by exposure.

[0346]

[0347] (In equations (a1) and (a2), R) A Each can be independently a hydrogen atom or a methyl group. R 1 and R 2 Each is an independent tertiary alkyl group having 4 to 6 carbon atoms. R 3 Each atom can be independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a single bond, a phenylene or naphthylene group, or a linker containing 1 to 12 carbon atoms selected from at least one of ester bonds, lactone rings, phenylene, and naphthylene groups. X 2 (These can be single bonds, ester bonds, or amide bonds.)

[0348] Examples of corrosion-resistant materials include the following.

[0349] A corrosion-resistant material comprising a polymer having repeating units as shown in formula (b1) or formula (b2).

[0350]

[0351] (In equations (b1) and (b2), R) AIt can be a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 It is a linear, branched, or cyclic alkylene group with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms. A portion of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group, or a group containing an lactone ring. Additionally, X 2 At least one hydrogen atom is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, wherein a portion of the methylene group constituting the alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each atom can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, but at least one of them must be a fluorine atom or a trifluoromethyl atom. Additionally, Rf... 1 and Rf 2 They can combine to form a carbonyl group. R 1 ~R 5 Each group is independently a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an alkynyl group with 2 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an aryloxyalkyl group with 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups may be substituted with hydroxyl, carboxyl, halogen, oxo, cyano, amide, nitro, sulopentalide, sulfonic acid, or a group containing a sulfonate. A portion of the methylene group constituting these groups may be substituted with ether, ester, carbonyl, carbonate, or sulfonate groups. Additionally, R... 1 With R 2 They can combine with the sulfur atoms they are bonded to to form rings.

[0352] A corrosion resist material comprising a base resin, said base resin comprising a polymer containing repeating units as shown in formula (a).

[0353]

[0354] (In equation (a), R) A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an acid-instable group. R 2 It is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a single bond or a phenylene group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms that may contain an ester group or an lactone ring. X 2 It can be -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. Where m+u is an integer from 1 to 4.

[0355] A photoresist composition that generates acid upon exposure, thereby altering its solubility in a developer solution through the action of the acid. It contains a substrate component (A) whose solubility in the developer changes due to the action of acid, and a fluorinated additive component (F) that exhibits decomposition properties in alkaline developers. The above-mentioned fluorinated additive component (F) contains a fluoropolymer component (F1), which has a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0356]

[0357] In the formula (f2-r-1), Rf 21 Each can be independently a hydrogen atom, alkyl group, alkoxy group, hydroxy group, hydroxyalkyl group, or cyano group. n” is an integer from 0 to 2. For bonding.

[0358] The above structural unit (f1) includes the structural unit shown in the following general formula (f1-1) or the structural unit shown in the following general formula (f1-2).

[0359]

[0360] In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. X is a divalent linker without an acid-dissociating site. A aryl It is a divalent aromatic cyclic group that can have substituents. X 01 It is a single-bond or divalent linker. R 2 Each is an organic group containing a fluorine atom.

[0361] As a corrosion resist composition, it can also be a corrosion resist containing metal.

[0362] Metal-containing photoresists are also called metal oxide photoresists (MOR), with tin oxide photoresists being a representative example.

[0363] As a metal oxide resist material, examples include, for instance, the coating composition disclosed in Japanese Patent Application Publication No. 2019-113855, which contains a metal oxygen-hydroxyl network having organic ligands through metal carbon bonds and / or metal carboxylate bonds.

[0364] In one example of a resist containing a metal, a peroxide ligand is used as a radiation sensitivity stabilizing ligand. Details of peroxide-based metal oxy-hydroxy compounds are described in patent documents such as those described in paragraph

[0011] of Japanese Laid-Open Patent Publication No. 2019-532489. As such patent documents, for example, U.S. Patent No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Patent No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738 can be cited.

[0365] A coating material comprising a metal oxy-hydroxy network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0366] Inorganic oxygen / hydroxy-based composition.

[0367] A coating solution comprising an organic solvent, a first organometallic composition, and a hydrolyzable metal compound, the first organometallic composition being represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R’ n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R’ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; the hydrolyzable metal compound is represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof).

[0368] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), the solution containing from about 0.0025 M to about 1.5 M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to tin at a secondary or tertiary carbon atom.

[0369] An aqueous inorganic pattern-forming precursor solution comprising a mixture of water, metal lower oxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group.

[0370] Other examples of metal-containing corrosion inhibitors include the compositions described in Japanese Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Application Publication No. 2020-122959, Japanese Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229.

[0371] These contents are incorporated into this specification to the same extent as all contents are expressly stated.

[0372] There are no particular limitations on the method of forming a metal-containing resist film from a metal-containing resist. For example, a method can be used to coat a coating type resist material (a composition for forming a metal-containing resist film) as a metal-containing resist and then fire it.

[0373] Alternatively, a metal-containing resist film can also be formed by vapor deposition. As a method for forming a metal-containing resist film by vapor deposition, the method described in Japanese Patent Application Publication No. 2017-116923 can be cited as an example. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein by reference to the entire contents thereof. It should be noted that in Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film of the present invention is referred to as a film containing metal oxides.

[0374] Irradiation with light or electron beams is performed, for example, by a mask (photomask) used to form a prescribed pattern. Examples include i-rays, KrF excimer lasers, ArF excimer lasers, EUV (ultra-ultraviolet) or EB (electron beam). The resist underlayer film formation composition of the present invention is preferably suitable for EB (electron beam) or EUV (ultra-ultraviolet: 13.5 nm) irradiation, and more preferably suitable for EUV (ultra-ultraviolet) exposure.

[0375] There are no particular restrictions on the irradiation energy of the electron beam and the amount of light exposure.

[0376] It can also be baked after irradiation with light or electron beams and before development (PEB: Post Exposure Bake).

[0377] There are no particular limitations on the baking temperature, but it is preferably 60°C to 260°C, more preferably 70°C to 180°C, and particularly preferably 75°C to 110°C.

[0378] There are no particular restrictions on the baking time, but it is preferred to be 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0379] For example, alkaline developing solutions or organic solvents can be used for developing.

[0380] Examples of developing temperatures include 5°C to 50°C.

[0381] Examples of development times include 10 seconds to 300 seconds.

[0382] As an alkaline developer, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyl diethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropanol and nonionic surfactants can be added to the above-mentioned alkaline aqueous solutions. Among these, aqueous solutions of quaternary ammonium salts are preferred, and aqueous solutions of tetramethylammonium hydroxide and choline are more preferred. Furthermore, surfactants can be added to these developers. Alternatively, development can be performed using organic solvents such as butyl acetate instead of an alkaline developer, resulting in partial development without increasing the alkaline dissolution rate of the photoresist.

[0383] As a developer for a metal-containing photoresist, an organic solvent can be used, and development is performed by passing the developer (solvent) after irradiation with light or an electron beam. Thus, for example, when using a negative metal-containing photoresist film, the unexposed portions of the metal-containing photoresist film are removed, forming a pattern of the metal-containing photoresist film.

[0384] Examples of organic solvents used as developers 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 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-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Butylacetyl 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. Examples include 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, 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 can also be added to these developing solutions.

[0385] Next, the formed resist pattern is used as a mask to etch the underlying resist film. Etching can be dry etching or wet etching, but dry etching is preferred.

[0386] When the aforementioned inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed; when the aforementioned inorganic film is not formed on the surface of the semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, by processing the semiconductor substrate using a known method (such as dry etching), a semiconductor device can be manufactured.

[0387] Example

[0388] The following examples illustrate the content of the present invention in detail, but the present invention is not limited to these examples.

[0389] The weight-average molecular weight (Mw) of the polymers shown in the following synthetic examples is based on the results determined by gel permeation chromatography (GPC). The determination used... The GPC apparatus manufactured by the company is tested under the following conditions.

[0390] • Measuring apparatus: HLC-8020GPC (trade name) Co., Ltd.)

[0391] • GPC columns: TSKgel G2000HXL; 2 columns, G3000HXL; 1 column, G4000HXL; 1 column [Product Name] (All are...) Co., Ltd.)

[0392] Column temperature: 40℃

[0393] Solvent: Tetrahydrofuran (THF)

[0394] • Flow rate: 1.0 mL / min

[0395] Standard sample: polystyrene ( Co., Ltd.)

[0396] <Synthesis example 1>

[0397] 63.64 g of glycidyl methacrylate and 6.36 g of 2,2'-azobisisobutyronitrile were dissolved in 130.00 g of propylene glycol monomethyl ether acetate. After nitrogen purging of the reaction vessel, the solution was heated and stirred at 100 °C for approximately 24 hours. The reaction solution was added dropwise to isopropanol, and the precipitate was recovered by filtration and then dried under reduced pressure at 40 °C to recover polymer 1. The weight-average molecular weight (Mw) obtained by GPC conversion to polystyrene was 3700. The polymer obtained in this synthetic example has the structural unit shown in formula (1').

[0398]

[0399] <Synthesis example 2>

[0400] The following were prepared using 1.71 g of polyglycidyl methacrylate synthesized in Synthesis Example 1, 4.17 g of 4-((6-(methacryloyloxy)hexyl)oxy)cinnamic acid, 0.006 g of hydroquinone, and tetrabutyl bromide. 0.12 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were added to the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 90°C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis showed that the polymer in the obtained solution had a weight-average molecular weight of 12,000 converted from standard polystyrene. The polymer obtained in this synthesis example has the structural unit shown in formula (1a).

[0401]

[0402] <Synthesis example 3>

[0403] 1.81 g of polyglycidyl methacrylate synthesized in Synthesis Example 1, 4.06 g of 4-{[6-(methacryloyloxy)hexyl]oxy}benzoic acid, 0.007 g of hydroquinone, and tetrabutyl bromide were prepared. 0.12 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were added to the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 90°C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution, converted from standard polystyrene, was 10600. The polymer obtained in this synthesis example has the structural unit shown in formula (1b) below.

[0404]

[0405] <Synthesis example 4>

[0406] 1.39 g of polyglycidyl methacrylate synthesized using Synthesis Example 1, 4.51 g of 4-[[4-[[6-[(1-oxo-2-propenyl)oxy]hexyl]oxy]benzoyl]oxy]phenylpropionic acid, 0.005 g of hydroquinone, and tetrabutyl bromide were prepared. 0.09 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were added to the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 90°C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution, converted from standard polystyrene, was 11700. The polymer obtained in this synthesis example has the structural unit shown in formula (1c).

[0407]

[0408] <Synthesis example 5>

[0409] 2.52 g of polyglycidyl methacrylate, 3.29 g of 4-hydroxyphenyl methacrylate, 0.009 g of hydroquinone, and tetrabutyl bromide synthesized using Synthesis Example 1 were used. 0.17 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were added to the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 90°C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution, converted from standard polystyrene, was 18400. The polymer obtained in this synthesis example has the structural unit shown in formula (1d).

[0410]

[0411] <Synthesis example 6>

[0412] The following ingredients were added: 1.09 g of cresol phenolic varnish type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 1.85 g of 4-((6-(methacryloyloxy)hexyl)oxy)cinnamic acid, 0.01 g of hydroquinone, and tetrabutyl bromide. 0.05 g of propylene glycol monomethyl ether was added to 23.67 g of propylene glycol monomethyl ether in the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even after cooling to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution was 6000 when converted to standard polystyrene. The polymer obtained in this synthesis example has the structural unit shown in formula (1e).

[0413]

[0414] <Synthesis Example 7>

[0415] The alicyclic epoxy resin NER-HM (co.) 1.00 g of (prepared), 5.50 g of 4-{[6-(methacryloyloxy)hexyl]oxy}benzoic acid, 0.05 g of hydroquinone, and tetrabutyl bromide 0.19 g of propylene glycol monomethyl ether was added to 37.02 g of propylene glycol monomethyl ether in the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution was 7180 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural unit shown in formula (1f) below.

[0416]

[0417] <Synthesis example 8>

[0418] The alicyclic epoxy resin NER-HM (co.) 1.00 g of (prepared), 7.91 g of 4-[[4-[[6-[(1-oxo-2-propenyl)oxy]hexyl]oxy]benzoyl]oxy]phenylpropionic acid, 0.05 g of hydroquinone, and tetrabutyl bromide 0.19 g of propylene glycol monomethyl ether was added to 46.65 g of propylene glycol monomethyl ether in the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 105 °C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even after cooling to room temperature and showed good solubility in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution was 8240 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural unit shown in the following formula (1 g).

[0419]

[0420] <Synthesis Example 9>

[0421] 3.00 g of polyglycidyl methacrylate synthesized in Synthesis Example 1, 2.38 g of propionic acid, and tetrabutyl bromide were used. 0.21 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were added to the reaction vessel and dissolved. After nitrogen purging of the reaction vessel, the reaction was carried out at 80°C for 24 hours to obtain a polymer solution. This polymer solution did not produce turbidity even when cooled to room temperature and showed good solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. GPC analysis showed that the weight-average molecular weight of the polymer in the obtained solution, converted from standard polystyrene, was 10426. The polymer obtained in this synthesis example has the structural unit shown in formula (2a) below.

[0422]

[0423] (Preparation of Composition 1 for Forming the Lower Layer of the Resist Film)

[0424] To 0.66 g of the polymer solution (solid content 13.1% by mass) obtained in Synthesis Example 2, add 0.43 g of a 5% by mass propylene glycol monomethyl ether solution of tetramethoxymethyl urea and pyridine phenolsulfonate. Dissolve 0.22 g of 1% propylene glycol monomethyl ether solution, 33 g of propylene glycol monomethyl ether, and 15 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 1 for forming the lower layer film of photoresist.

[0425] (Preparation of Composition 2 for Forming the Lower Layer of the Resist Film)

[0426] To 0.66 g of the polymer solution (solid content 13.0% by mass) obtained in Synthesis Example 3, add 0.43 g of a 5% by mass propylene glycol monomethyl ether solution of tetramethoxymethyl urea and pyridine phenolsulfonate. Dissolve 0.22 g of 1% propylene glycol monomethyl ether solution, 33 g of propylene glycol monomethyl ether, and 15 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 2 for forming the lower layer film of photolithography resist.

[0427] (Preparation of Composition 3 for Forming the Lower Layer of the Resist Film)

[0428] To 0.66 g of the polymer solution (solid content 13.0% by mass) obtained in Synthesis Example 4, add 0.43 g of a 5% by mass propylene glycol monomethyl ether solution of tetramethoxymethyl urea and pyridine phenolsulfonate. Dissolve 0.22 g of 1% propylene glycol monomethyl ether solution, 33 g of propylene glycol monomethyl ether, and 15 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 3 for forming the lower layer film of photolithography resist.

[0429] (Preparation of Composition 4 for Forming the Lower Layer of the Resist Film)

[0430] To 0.74 g of the polymer solution (solid content 10.05% by mass) obtained in Synthesis Example 5, add 0.37 g of a 5% by mass propylene glycol monomethyl ether solution of tetramethoxymethyl urea and pyridine phenolsulfonate. Dissolve 0.19 g of 1% propylene glycol monomethyl ether solution, 34 g of propylene glycol monomethyl ether, and 14 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 4 for forming the lower layer of the resist film.

[0431] (Preparation of composition 5 for forming the lower layer of the resist film)

[0432] To 0.74 g of the polymer solution (solid content 10.38% by mass) obtained in Synthesis Example 6, add 0.37 g of a 5% by mass propylene glycol monomethyl ether solution of tetramethoxymethyl urea and pyridine phenolsulfonate. Dissolve 0.19 g of a 1% (w / w) propylene glycol monomethyl ether solution, 34 g of propylene glycol monomethyl ether, and 14 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 5 for forming the lower layer film of photolithography resist.

[0433] (Preparation of Composition 6 for Forming the Lower Layer of the Resist Film)

[0434] To 0.43 g of the polymer solution (solid content 17.0% by mass) obtained in Synthesis Example 7, tetramethoxymethylglyoxal (Japan) was added. (manufactured by) 0.37 g of 5% propylene glycol monomethyl ether solution and pyridine phenolsulfonate Dissolve 0.18 g of a 1% (w / w) propylene glycol monomethyl ether solution, 34 g of propylene glycol monomethyl ether, and 14 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 6 for forming the lower layer film of photolithography resist.

[0435] (Preparation of composition 7 for forming the lower layer film of the resist)

[0436] To 0.46 g of the polymer solution (solid content 16.3% by mass) obtained in Synthesis Example 8, tetramethoxymethylglyoxal (Japan) was added. (manufactured by) 0.37 g of 5% propylene glycol monomethyl ether solution and pyridine phenolsulfonate Dissolve 0.19 g of 1% propylene glycol monomethyl ether solution, 34 g of propylene glycol monomethyl ether, and 15 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 7 for forming the lower layer film of photolithography resist.

[0437] (Preparation of composition 8 for forming the lower layer of the resist film)

[0438] To 0.41 g of the polymer solution (solid content 18.5% by mass) obtained in Synthesis Example 9, tetramethoxymethylglyoxal (Japan) was added. (manufactured by) 0.38 g of 5% propylene glycol monomethyl ether solution and pyridine phenolsulfonate Dissolve 0.19 g of 1% propylene glycol monomethyl ether solution, 33 g of propylene glycol monomethyl ether, and 15 g of propylene glycol monomethyl ether acetate. Then filter the solution using a polyethylene microfilter with a pore size of 0.05 μm to prepare composition 8 for forming the lower layer film of photolithography resist.

[0439] <Example of Metal Oxide Corrosion Resist Modification>

[0440] (Preparation of metal oxide corrosion resist composition)

[0441] 0.16 g of monobutyltin oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 9.84 g of 4-methyl-2-pentanol. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare metal oxide resist composition 1.

[0442] <Example 1>

[0443] (Evaluation of resist pattern formation)

[0444] [Formation of metal oxide resist patterns using an electron beam drawing device]

[0445] The resist underlayer film formation composition 1 was coated onto a silicon wafer using a spin coater. The silicon wafer was then baked on a hot plate at 215°C for 60 seconds to obtain a resist underlayer film with a thickness of 5 nm. The metal oxide resist composition 1 prepared according to the metal oxide resist preparation example was then spin-coated onto this resist underlayer film, and heated at 100°C for 60 seconds to form a metal oxide resist film with a thickness of 26 nm. Then, to form the target pattern, exposure was performed under specified conditions using an electron beam tracing apparatus (ELS-G130). After exposure, baking was performed at 260°C for 60 seconds (PEB), followed by development with a developer (5% by mass propylene glycol monomethyl ether acetate solution of acetic acid), forming a line and void pattern with a CD size of 22 nm and a spacing of 44 nm. The length of the resist pattern was measured using a scanning electron microscope (Hitachi, Inc.). (Prepared by CG4100). An observation photograph of the resist pattern formed in Example 1 is shown. Figure 1 .

[0446] <Examples 2-7>

[0447] Instead of composition 1 for forming a photoresist underlayer film, compositions 2 to 7 for forming a photoresist underlayer film were used. Otherwise, a line and void pattern with a CD size of 22 nm and a spacing of 44 nm was formed by the same method as in Example 1.

[0448] <Comparative Example 1>

[0449] Instead of composition 1 for forming a photoresist underlayer film, composition 8 for forming a photoresist underlayer film was used. Otherwise, a line and void pattern with a CD size of 22 nm and a spacing of 44 nm was formed by the same method as in Example 1.

[0450] Regarding the photoresist patterns obtained in Examples 1-7 and Comparative Example 1, observing from the top of the pattern, the amount of charge forming a 22nm line / 44nm spacing (line to gap (L / S=1 / 1)) was taken as the optimal irradiation energy, and the irradiation energy (mC / cm) at this point was confirmed. 2 The results are shown in Table 1.

[0451] [Table 1]

[0452] According to Table 1, compared with Comparative Example 1, Examples 1-7 can reduce the irradiation energy required for pattern formation and increase the sensitivity of the resist. Therefore, when this process is applied, the composition for forming the lower film is useful for resist pattern formation.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) and a solvent, said polymer (A) having one or more polymerizable multiple bonds selected from carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds and carbon-nitrogen triple bonds and an aromatic hydrocarbon ring in its side chain.

2. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a group represented by the following formula (A), In formula (A), L 1 L represents a single bond or linker. 2 L represents a divalent group having the aromatic hydrocarbon ring. 3 This refers to a monovalent group having the aforementioned polymerizable multiple bonds. This represents a bonding bond.

3. The composition for forming a resist underlayer film according to claim 2, wherein the group represented by formula (A) contains L 2 It is represented by the following formula (b), In equation (b), W 1 W 2 and W 3 Each is independently a single bond, -O-, -C(=O)-O-, -OC(=O-, -OC(=O)-CH2-, -C(=O)-N(R')-, or -N(R')-C(=O-); W 2 When the number is two or more, each W 2 They can be the same or different; R' represents an alkyl group with 1 to 6 hydrogen atoms. Q is a single bond, or an alkylene group with 1 to 10 carbon atoms, or an alkenyl sub-chain with 2 to 10 carbon atoms, wherein some or all of the hydrogen atoms of the alkylene or alkenyl sub-chain can be replaced by halogen atoms. L b This refers to a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linker formed by substituting one or more non-adjacent -CH2- atoms of an alkylene group having 1 to 12 carbon atoms with -O-, -S-, -C(=O)-O-, or OC(=O)-, wherein some or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms. Q 1 It is a single bond, a phenylene, a naphthylene, or a divalent alicyclic hydrocarbon group with 5 to 8 carbon atoms, wherein some or all of the hydrogen atoms of the phenylene and naphthylene groups may be substituted by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkyl carbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; Q 1 When the number of Q is two or more, each Q 1 They can be the same or different. R b It is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group. p is 0, 1, 2, 3 or 4. m is 0 or 1. n1 is 0, 1, 2, or 3. a and b represents a bonding bond. a and L 1 Combine, b and L 3 Combine.

4. The composition for forming a resist underlayer film according to claim 3, wherein the L 2 In the divalent group shown in formula (b), W 3 The combination with Q is any of the following combinations: W 3 It is a single key and Q is a single key, W 3 It is a single bond and Q is an alkylene group with 1 to 10 carbon atoms, and W 3 It is a single bond and Q is a sub-alkenyl group with 2 to 10 carbon atoms.

5. The composition for forming a resist underlayer film according to claim 3, wherein the L 2 In the divalent group shown in formula (b), Q 1 With W 2 The combination is any of the following combinations: Q 1 It is a single key and W 2 Q is a single bond and n1 is 1. 1 It is a phenylene and W 2 It is -C(=O)-O-.

6. The composition for forming a resist underlayer film according to claim 3, wherein the L 2 In the divalent group shown in formula (b), L b With W 1 The combination is any of the following combinations: L b It is a single key and W 1 For single bond, L b It is an alkylene group having 1 to 10 carbon atoms and W 1 For -OC(=O)-CH2-, and L b It is an alkylene group having 1 to 10 carbon atoms and W 1 It is -O-.

7. The composition for forming a resist underlayer film according to claim 2, wherein the group represented by formula (A) contains L 1 The connecting base has a structural part as shown in formula (t1) or formula (t2) below. In the formula, 1 represents L in equation (A) 2 Bonds on opposite sides of one side, 2 represents L in equation (A) 2 The binding bond of the combination.

8. The composition for forming a resist underlayer film according to claim 2, wherein the group represented by formula (A) contains L 3 The monovalent group with polymerizable multiple bonds has the structural site shown in formula (u1) or formula (u2) below. In the formula, L in equation (A) 2 The binding bond of the combination.

9. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a structural unit represented by the following formula (1), In equation (1), R 1 L represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 11 L represents a single bond or linker. 12 L represents a divalent group having the aromatic hydrocarbon ring. 13 This refers to a monovalent group having the aforementioned polymerizable multiple bonds.

10. The composition for forming a resist underlayer film according to claim 9, wherein in the structural unit shown in formula (1), the L 11 The connection base is represented by the following formula (L1-1) or the following formula (L1-2). In the formula, 1 indicates the combination with R in equation (1) 1 The carbon atoms are bonded together by bonds. 2 represents L in equation (1) 12 The binding bond of the combination.

11. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has a structural unit represented by the following formula (2), In equation (2), R a Indicates a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; Ar indicates a benzene ring, naphthalene ring, or anthracene ring; L X L represents a single bond or a divalent group that can have substituents. 21 L represents a single bond or linker. 22 L represents a divalent group having the aromatic hydrocarbon ring. 23 This represents a monovalent group having the polymerizable multiple bonds, where n1 is an integer from 0 to 3.

12. The composition for forming a resist underlayer film according to claim 11, wherein in the structural unit shown in formula (2), the L 21 The connection base is represented by the following equation (L1-12), In the formula, 1 represents the bonding bond that binds to Ar in equation (2). 2 represents L in equation (1) 22 The binding bond of the combination.

13. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) has the structural unit shown in formula (3). In equation (3), L 31 L represents a single bond or linker. 32 L represents a divalent group having the aromatic hydrocarbon ring. 33 This refers to a monovalent group having the aforementioned polymerizable multiple bonds.

14. The composition for forming a resist underlayer film according to claim 13, wherein in the structural unit shown in formula (3), the L 31 The connection base is represented by the following equation (L1-13), In the formula, 1 represents the bonding bond with the alicyclic hydrocarbon in formula (3). 2 represents L in equation (3) 32 The binding bond of the combination.

15. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent.

16. A resist underlayer film, which is a cured product of the resist underlayer film forming composition according to any one of claims 1 to 15.

17. A laminated body comprising: Semiconductor substrates, and The resist underlayer film as described in claim 16.

18. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 15; and The process of forming a resist film on the lower resist film.

19. A method for forming a pattern, comprising the following steps: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 15; The process of forming a resist film on the lower resist film; The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern; and The process of using the resist pattern as a mask to etch the underlying resist film.

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