Compound

Abstract

To provide a compound suitable for a resist underlay film-forming composition that is insoluble in resist solvents and boasts superior optical constants and enhanced etching rates, with the composition offering superior embeddability and flatness for stepped substrates.SOLUTION: The present invention provides a compound represented by the general formula (II), wherein, m is an integer of 1 to 30; m pieces of T each represent a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent aromatic or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group, or an alkylene group and may be substituted with an alkyl group or an alkenyl group; m pieces of G1 and G2 each represent the following (i) or the like; and Z1 and Z2 independently represent a hydroxy group, an epoxy group or a hydrogen atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist underlayer film-forming composition suitable for lithography in semiconductor substrate processing, a resist underlayer film obtained from the resist underlayer film-forming composition, a method for producing a patterned substrate using the resist underlayer film-forming composition, and a method for producing a semiconductor device. [Background technology]

[0002] Conventionally, microfabrication by lithography using a photoresist composition has been performed in the manufacture of semiconductor devices. This microfabrication method involves forming a thin film of the photoresist composition on a substrate to be processed, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developing the thin film, and etching the substrate, such as a silicon wafer, using the resulting photoresist pattern as a protective film. In recent years, with the increasing integration density of semiconductor devices, the wavelength of the actinic rays used has been shortened from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). Furthermore, with the aim of achieving even finer microfabrication, lithography techniques using extreme ultraviolet (EUV, 13.5 nm) or electron beams (EB) as actinic rays have also been developed.

[0003] In the lithography process, when a resist layer on a substrate is exposed to an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, a known problem occurs in that a resist pattern having the desired shape cannot be formed due to the effects of standing waves caused by the ultraviolet laser being reflected off the substrate surface.To solve this problem, a resist underlayer film (anti-reflective film) is provided between the substrate and the resist layer.

[0004] In order to prevent mixing with the resist layer laminated on top of such a photoresist, the resist underlayer film formed between the photoresist and the substrate to be processed is generally formed as a thermosetting crosslinked film that does not mix with the resist by being applied to the substrate and then undergoing a baking process.

[0005] It is known that various resins are used as compositions for forming resist underlayer films. For example, Patent Documents 1 and 2 disclose photoresist underlayer film-forming materials containing resins having repeating units formed by novolakization of a compound having a bisphenol group. Furthermore, Patent Document 3 discloses a spin-coatable antireflective coating composition containing a polymer having three or more fused aromatic rings in the polymer main chain.

[0006] However, when there are steps on the underlying substrate to be processed, or when densely patterned areas and areas without patterns exist on the same wafer, it is necessary to flatten the film surface with an underlayer film. Resins suitable for such purposes have been proposed (Patent Document 4).

[0007] On the other hand, in order to form such a thermosetting film, a resist underlayer film-forming composition contains, in addition to the polymer resin as the main component, a crosslinking compound (crosslinking agent) and a catalyst (crosslinking catalyst) for accelerating the crosslinking reaction. Regarding the issue of flattening the film surface by the underlayer film, the investigation of these components has not yet been sufficient. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-259249 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-316282 [Patent Document 3] Special Publication No. 2010-528334 [Patent Document 4] WO 2014 / 024836 A1 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a composition for forming a resist underlayer film that is insoluble in a resist solvent, has good optical constants, and a high etching rate, and that has excellent filling properties and planarization properties for uneven substrates. [Means for solving the problem]

[0010] The present invention encompasses the following. [1] (A) a crosslinkable compound represented by the following formula (I), and (D) Solvent A resist underlayer film-forming composition comprising: [ka] [In the formula, m is an integer of 1 to 30, When m=1, T is a single bond, a divalent to hexavalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent to hexavalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; G 1 , G 2 , and G that exists as the valence of T increases to 3 or more 3 , G 4 , G 5 , G 6 are each independently [ka] or [ka] and n's are each independently an integer of 1 to 8, n R's each independently represent a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group; Each A is independently a C-C alkylene group optionally interrupted by an alkylene group.18 is an aryl group, Z 1 , Z 2 , and Z that exists as the valence of T increases to 3 or more 3 , Z 4 , Z 5 , Z 6 each independently represents an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, or an aryl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group and which may be substituted with a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C1-C9 alkoxy group, an alkyl group, an alkenyl group or an alkynyl group. When m>1, m T's each represent a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; G 3 Z 3 , G 4 Z 4 , G 5 Z 5 , G 6 Z 6 does not exist, m Gs 1 , and G 2 are each independently [ka] or [ka] and n, R, and A are as defined above; Z 1 , and Z 2 each independently represents a hydroxy group, an epoxy group, or a hydrogen atom. [2] The resist underlayer film forming composition according to [1], wherein each A is independently a C6 aryl group optionally interrupted by an alkylene group. [3] The resist underlayer film-forming composition according to [1] or [2], further comprising (B) a film material capable of undergoing a crosslinking reaction with the crosslinkable compound (A). [4] The resist underlayer film-forming composition according to [3], wherein the crosslinkable film material (B) comprises at least one selected from the group consisting of a resin containing an aliphatic ring, a novolak resin, a polyether resin, a polyester resin, an acrylic resin, a methacrylic resin, and a compound different from the crosslinkable compound (A). [5] The novolak resin is represented by the following formula (1a), formula (1b), and formula (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (1b), two R 3 and two R 4 may be different from each other, two k's each independently represent 0 or 1, m0 represents an integer of 3 to 500, n0, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent a group represented by the following formula (2): [ka] (wherein two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are the same as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). The resist underlayer film forming composition according to [4], wherein the composition is represented by one or more of the repeating structural units represented by the following formula: [6] A compound different from the crosslinkable compound (A) is [ka] (in formula (2), each of two Ar represents an aryl group having at least one hydroxy group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond.) [7] The resist underlayer film forming composition according to [1] or [2], further comprising (C) an acid catalyst. [8] The resist underlayer film forming composition according to any one of [3] to [6], further comprising (C) an acid catalyst. [9] The resist underlayer film forming composition according to [8], wherein the crosslinkable compound (A) is represented by the following formula (1): [ka] [In the formula, V is [ka] or [ka] represents i is an integer from 2 to 6, i R's each independently represent a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group; each of the i n's independently represents an integer of 1 to 8; i A's each independently represent a C-C alkylene group optionally interrupted by an alkylene group; 18 is an aryl group, i Z's each independently represent an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, or an aryl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group and which may be substituted with a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C1-C9 alkoxy group, an alkyl group, an alkenyl group or an alkynyl group; T is a single bond, an i-valent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an i-valent aromatic group which may be interrupted by an oxygen atom or an alkylene group and which may be substituted with an alkyl group or an alkenyl group.

[10] The resist underlayer film-forming composition according to [9], wherein each Z is independently an aryl group which may be interrupted by an alkyl group, an oxygen atom, a nitrogen atom, or a carbonyl group, and which may be substituted with a hydroxyl group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C1-C9 alkoxy group, an alkyl group, an alkenyl group, or an alkynyl group.

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

[10] .

[12] A method for producing a patterned substrate, comprising the steps of: applying the resist underlayer film-forming composition according to any one of [1] to

[10] onto a semiconductor substrate and curing it to form a resist underlayer film; applying a resist onto the resist underlayer film and baking it to form a resist film; exposing the resist underlayer film and the semiconductor substrate coated with the resist; and developing and patterning the resist film after exposure.

[13] The method for producing a patterned substrate according to

[12] , wherein the curing is carried out by baking.

[14] The method for producing a patterned substrate according to

[12] , wherein after baking, the curing is carried out by irradiating with ultraviolet light.

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

[10] ; forming a resist film thereon; forming a resist pattern by irradiating with light or an electron beam and developing; etching the underlayer film using the resist pattern; and processing a semiconductor substrate using the patterned underlayer film.

[16] A compound represented by the following formula (II): [ka] In the formula, m is an integer of 1 to 30, m T's each represent a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; m Gs 1 , and G 2 are each independently [ka] or [ka] and n's are each independently an integer of 1 to 8, n R's each independently represent a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group; Each A is independently a C-C alkylene group optionally interrupted by an alkylene group. 18 is an aryl group, Z 1 , and Z 2 each independently represents a hydroxy group, an epoxy group, or a hydrogen atom.

[17] Compounds represented by the following formulas (1-21) to (1-25): [ka] (In the formula, each m is independently an integer of 1 to 20, Each r is independently an integer of 0 to 5. [Effects of the Invention]

[0011] The crosslinking compound having a specific chemical structure according to the present invention undergoes a gradual crosslinking reaction with film materials. Therefore, when a resist underlayer film-forming composition containing the crosslinking compound according to the present invention is applied to a fine pattern on a substrate, the fluidity of the composition is maintained for a certain period of time until three-dimensionalization by crosslinking progresses. As a result, the resist underlayer film-forming composition according to the present invention can fill the fine pattern of an uneven substrate without gaps. Furthermore, a resist underlayer film formed by applying the resist underlayer film-forming composition according to the present invention to an uneven substrate and baking it can further reduce the film thickness difference (iso-dense bias) between the patterned areas (dense areas (patterned areas)) and the pattern-free areas (open areas (non-patterned areas)) of a coating formed thereon. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Resist underlayer film-forming composition] The resist underlayer film-forming composition according to the present invention comprises: (A) a crosslinkable compound represented by the following formula (I), and (D) Solvent Includes.

[0013] Optionally, the resist underlayer film-forming composition according to the present invention comprises: (B) a membrane material capable of crosslinking with the crosslinkable compound (A), and / or (C) Acid catalyst It may further include:

[0014] Furthermore, the resist underlayer film forming composition according to the present invention may contain additives such as an acid generator and a surfactant, if necessary.

[0015] [(A) Crosslinkable compound] The crosslinkable compound (A) used in the present invention is represented by the following formula (I). [ka] [In the formula, m is an integer of 1 to 30, When m=1, T is a single bond, a divalent to hexavalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent to hexavalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; G 1 , G 2 , and G that exists as the valence of T increases to 3 or more 3 , G 4 , G 5 , G 6 are each independently [ka] or [ka] and n's are each independently an integer of 1 to 8, n R's each independently represent a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group; Each A is independently a C-C alkylene group optionally interrupted by an alkylene group. 18 is an aryl group, Z 1 , Z 2 , and Z that exists as the valence of T increases to 3 or more 3 , Z 4 , Z 5 , Z6 each independently represents an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, or an aryl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group and which may be substituted with a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C1-C9 alkoxy group, an alkyl group, an alkenyl group or an alkynyl group. When m>1, m T's each represent a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; G 3 Z 3 , G 4 Z 4 , G 5 Z 5 , G 6 Z 6 does not exist, m Gs 1 , and G 2 are each independently [ka] or [ka] and n, R, and A are as defined above; Z 1 , and Z 2 each independently represents a hydroxy group, an epoxy group, or a hydrogen atom.

[0016] Preferably, the crosslinkable compound (A) used in the present invention is represented by the following formula (II): [ka] In the formula, m is an integer of 1 to 30, m T's each represent a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or a divalent aromatic group or unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom, a carbonyl group or an alkylene group and which may be substituted with an alkyl group or an alkenyl group; m Gs 1 , and G 2 are each independently [ka] or [ka] and n's are each independently an integer of 1 to 8, n R's each independently represent a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group; Each A is independently a C-C alkylene group optionally interrupted by an alkylene group. 18 is an aryl group, Z 1 , and Z 2 each independently represents a hydroxy group, an epoxy group, or a hydrogen atom.

[0017] Preferably, the crosslinkable compound (A) used in the present invention is represented by the following formula (1): [ka] [In the formula, V is [ka] or [ka] represents i is an integer from 2 to 6, i R's each independently represent a hydrogen atom, an oxygen atom, a nitrogen atom, or an alkyl group optionally interrupted by a carbonyl group; each of the i n's independently represents an integer of 1 to 8; i A's each independently represent a C-C alkylene group optionally interrupted by an alkylene group; 18 is an aryl group, i Z's each independently represent an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, an aryl group optionally interrupted by an oxygen atom, a nitrogen atom or a carbonyl group and optionally substituted with a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C1-C9 alkoxy group, an alkyl group, an alkenyl group or an alkynyl group; T is a single bond, an i-valent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an i-valent aromatic group which may be interrupted by an oxygen atom or an alkylene group and which may be substituted with an alkyl group or an alkenyl group.

[0018] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, an n-pentyl group, a 1-methyln-butyl group, a 2-methyln-butyl group, a 3-methyln-butyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyln-propyl group, a 1-ethyln-propyl group, a cyclopentyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a 3-methylcyclopropyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyln-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methylcyclopropyl group, a 2 ... ethyl-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 ethyl, 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-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-i-propylcyclopropyl, 2-i-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,Examples include 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0019] The aryl group includes a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, etc. Preferably, it is a C6-C 18 Aryl groups, more preferably C6-C 14 Aryl groups, more preferably C6-C 10 An aryl group, most preferably a C6 aryl group. The aryl group which may be interrupted by an alkylene group or the like and which may be substituted by a hydroxy group or the like is preferably an aryl group which may be interrupted by an alkylene group, an oxygen atom, a nitrogen atom or a carbonyl group, more preferably an aryl group which is interrupted by a carbonyl group and substituted by an alkyl group. For example, C1-C 10 Examples thereof include an alkylphenylcarbonyl group.

[0020] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n- Examples of the alkoxy group include pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy. C1-C9 alkoxy groups are preferred, C1-C6 alkoxy groups are more preferred, and C1-C3 alkoxy groups are even more preferred.

[0021] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0022] Examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), butenyl, butadienyl, pentenyl, pentadienyl, cyclopentenyl, hexenyl, hexadienyl, hexatrienyl, and cyclohexenyl groups. Preferably, C2-C 10 It is preferably an alkenyl group, more preferably a C2-C8 alkenyl group, and even more preferably a C2-C6 alkenyl group.

[0023] Examples of the alkynyl group include an ethynyl group (acetynyl group), a 1-propynyl group, a 2-propynyl group (propargyl group), a butynyl group, a pentynyl group, a pent-3-en-1-ynyl group, a hexynyl group, and a hex-2-en-4-ynyl group. 10 It is preferably an alkynyl group, more preferably a C2-C8 alkynyl group, and even more preferably a C2-C6 alkynyl group.

[0024] The saturated hydrocarbon group refers to a group obtained by removing any number of hydrogen atoms from a saturated hydrocarbon compound.

[0025] Aromatic groups generally refer to groups derived from organic compounds having a 4n+2 π-electron system, such as substituted or unsubstituted benzene, naphthalene, biphenyl, furan, thiophene, pyrrole, pyridine, indole, quinoline, and carbazole.

[0026] Examples of the saturated hydrocarbon group which may be interrupted by an aromatic ring include alkylene groups interrupted by phenylene and alkoxyphenylene.

[0027] The alkylene group refers to a group obtained by removing any one hydrogen atom from the alkyl group described above, and examples thereof include a methylene group, an ethylene group, a propylene group, a cyclopropylene group, a butylene group, a cyclobutylene group, a pentylene group, a cyclopentylene group, a hexylene group, and a cyclohexylene group.

[0028] The aromatic group which may be interrupted by oxygen atoms or the like and may be substituted by alkyl groups or the like is preferably an arylene group interrupted by an alkylene group and substituted by an alkenyl group, an arylene group substituted by an alkyl group, an arylene group interrupted by an oxygen atom, and an arylene group interrupted by an alkylene group and substituted by an alkyl group. Examples thereof include an allylphenylene group interrupted by a propylene group, a methyl-substituted biphenylene group, a naphthylene group interrupted by an oxygen atom, a tolylene group and a naphthylene group interrupted by a methylene group, etc.

[0029] The unsaturated cyclic hydrocarbon group, which may be interrupted by an oxygen atom or the like and may be substituted by an alkyl group or the like, is preferably a non-aromatic unsaturated cyclic hydrocarbon group, more preferably a divalent non-aromatic unsaturated cyclic hydrocarbon group. Examples include a cyclopentenediyl group or a cyclohexenediyl group, which may be substituted by an alkyl group or an alkenyl group (e.g., a vinyl group). These are preferably interrupted by an oxygen atom, a carbonyl group, or an alkylene group, and more preferably by a carbonyl group.

[0030] Specific examples of the crosslinkable compound represented by formula (I) used in the present invention are as follows: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In formula (1-10), m represents an integer of 0 to 3.) [ka] [ka] (In the formula, each m is independently an integer of 1 to 20, Each r is independently an integer of 0 to 5.

[0031] The above formulas (1-1) to (1-11) are also specific examples of the crosslinkable compound represented by formula (1) used in the present invention. The above formulas (1-21) to (1-25) are also specific examples of the crosslinkable compound represented by formula (II) used in the present invention.

[0032] The content of the crosslinkable compound (A) in the resist underlayer film-forming composition according to the present invention is usually 0.01 to 50 mass %, preferably 0.01 to 40 mass %, more preferably 0.1 to 30 mass %, based on the total solid content.

[0033] The compound (A) represented by the above formula (I) when m is 1, i.e., the crosslinkable compound (A) represented by the above formula (1), can be obtained by reacting a compound having i hydroxy groups represented by the following formula (101) with a glycidyl ether compound represented by the following formula (102). [ka] [ka] wherein V, i, R, n, A, Z, and T are as defined above.

[0034] The crosslinkable compound (A) represented by the above formula (1) can be obtained by reacting a compound having i glycidyl ether groups represented by the following formula (103) with a hydroxy compound represented by the following formula (104). [ka] [ka] wherein V, i, R, n, A, Z, and T are as defined above.

[0035] The compound (A) represented by the above formula (I) when m is greater than 1, i.e., the crosslinkable compound (A) represented by the above formula (II), can be obtained by reacting a diglycidyl ether compound represented by the following formula (105) with a dihydroxy compound represented by the following formula (106). [ka] [ka] [In the formula, R, n, A, and T are as defined above.]

[0036] The crosslinkable compound (A) represented by the above formula (II) can be obtained by reacting a dihydroxy compound represented by the following formula (107) with a diglycidyl ether compound represented by the following formula (108). [ka] [ka] [In the formula, R, n, A, and T are as defined above.]

[0037] Either reaction can be carried out in a suitable solvent in the presence of a suitable catalyst. Such a solvent is not particularly limited as long as it can uniformly dissolve the compound having i hydroxy groups represented by formula (101) and the glycidyl ether compound represented by formula (102), the compound having i glycidyl ether groups represented by formula (103) and the hydroxy compound represented by formula (104), the compound represented by formula (105) and the compound represented by formula (106), or the compound represented by formula (107) and the compound represented by formula (108), and does not inhibit the reaction or induce side reactions.

[0038] For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexanone, Examples of suitable solvents include butanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred.

[0039] Examples of the catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine, with ethyltriphenylphosphonium bromide being preferred.

[0040] In addition, in order to prevent unreacted acid, catalyst, inactivated catalyst, etc. from remaining in the reaction system, a cation exchange resin or anion exchange resin for catalysts can be used.

[0041] [(B) Membrane material capable of crosslinking with crosslinkable compound (A)] The membrane material optionally used in the present invention can be any material capable of undergoing a crosslinking reaction with the crosslinkable compound (A). The membrane material may be a polymer, an oligomer, or a low-molecular-weight compound having a molecular weight of 1,000 or less. Examples of crosslinkable groups present in the membrane material include, but are not limited to, hydroxyl groups, carboxyl groups, amino groups, and alkoxy groups.

[0042] (a) Examples of the film material capable of undergoing a crosslinking reaction include alicyclic epoxy polymers having a repeating structural unit represented by the following formula (1), as disclosed in WO 2011 / 021555 A1. [ka] (T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer, and E represents an epoxy group or an organic group having an epoxy group.)

[0043] E is a substituent on the aliphatic ring, and may be either an epoxy group directly bonded to the aliphatic group, or an organic group having an epoxy group (for example, a glycidyl group) bonded to the aliphatic group. The aliphatic ring is, for example, one in which 4 to 10 carbon atoms are linked in a ring, and particularly one in which 6 carbon atoms are linked in a ring. The aliphatic ring may have other substituents in addition to the substituent E (epoxy group or organic group having an epoxy group). Such substituents include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, halogen atoms, nitro groups, and amino groups. The alicyclic epoxy polymer represented by the formula (1) has a weight average molecular weight of 600 to 1,000,000, preferably 1,000 to 200,000. The number of repeating units of the alicyclic epoxy polymer (A) represented by the formula (1) is 2 to 3,000, or 3 to 600.

[0044] For example, the following polymers are exemplified. [ka]

[0045] (b) Examples of the crosslinkable membrane material include those represented by the following formula (1a), formula (1b), and formula (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (1b), two R 3 and two R4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (wherein two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are the same as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). Examples of the polymer include a polymer having one or more repeating structural units represented by the following formula:

[0046] Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0047] (c) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), R1 and R2 are each a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, or a carbon atom. an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 6 carbon atoms, to 40 aryl groups, and combinations thereof, and The alkyl group, the alkenyl group or the aryl group may be bonded by an ether bond, a ketone bond or an ester bond. represents a group which may contain a methyl group bond, R3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkene group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and a combination thereof; and the alkyl group, the alkenyl group, or the aryl group is selected from the group consisting of an ether bond, a keto bond, represents a group which may contain a methyl group bond or an ester bond, R4 may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group. represents an aryl group or a heterocyclic group having 6 to 40 carbon atoms; R5 is a hydrogen atom or a group substituted with a halogen group, a nitro group, an amino group, or a hydroxy group. an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, represents a group or a heterocyclic group, and R4 and R5 may together with the carbon atoms to which they are attached form a ring; and n1 and n2 are each an integer of 1 to 3.

[0048] Preferably, the polymer contains a unit structure in which, in the formula (1), R1, R2, R3, and R5 each represent a hydrogen atom, and R4 represents a phenyl group or a naphthyl group. Preferably, in the formula (1), R1, R2, and R3 each represent a hydrogen atom, and R4 and R5 together with the carbon atom to which they are attached form a fluorene ring, wherein the carbon atom is the 9-position carbon atom of the formed fluorene ring.

[0049] Preferably, the compound represented by the following formula (2) and / or formula (3): [ka] (In formula (2) and formula (3), R1, R2, R6, R7, and R8 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; and R4 and R5 may together with the carbon atoms to which they are attached form a ring; n1 and n2 are each an integer from 1 to 3, and n3 to n5 are each an integer of 1 to 4.

[0050] Preferably, in the formula (2) and / or formula (3), R1, R2, R3, R5, R6, R7, and R8 each represent a hydrogen atom, and R4 is a polymer containing a unit structure representing a phenyl group or a naphthyl group.

[0051] (d) Examples of the crosslinkable membrane material include polymers containing a unit structure formed from a reaction product of a fused heterocyclic compound and a bicyclic compound, as disclosed in WO 2013 / 005797 A1.

[0052] Preferably, the fused heterocyclic compound is a carbazole compound or a substituted carbazole compound. Preferably, the bicyclocyclic compound is dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3,8-diene, or substituted tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3,8-diene.

[0053] Preferably, the polymer is a polymer containing a unit structure represented by the following formula (1), a unit structure represented by the following formula (2), a unit structure represented by the following formula (3), or a combination thereof. [ka] (In the formula, R 1 ~R 14 are substituents of a hydrogen atom, each independently representing a halogen group, a nitro group, an amino group, or a hydroxy group, or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which may be substituted by such a group; Ar is an aromatic ring group having 6 to 40 carbon atoms; and n1, n2, n5, n6, n9, and n 10 , n 13 , n 14 and n 15 are integers from 0 to 3, and n3, n4, n7, n8, n 11 and n 12 are each an integer between 0 and 4.) Preferably, in the above formula (3), Ar is a phenyl group or a naphthyl group.

[0054] (e) Examples of crosslinkable membrane materials include those of formula (1): [ka] (In formula (1), A is a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B is a monovalent fused aromatic hydrocarbon ring group in which 2 to 4 benzene rings are fused.)

[0055] Preferably, A is a hydroxy-substituted phenylene group derived from benzenediol or benzenetriol. Preferably, A is a hydroxy-substituted phenylene group derived from catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol. Preferably, the fused aromatic hydrocarbon ring group of B is a naphthalene ring group, an anthracene ring group, or a pyrene ring group. Preferably, the fused aromatic hydrocarbon ring group of B has a halogen group, a hydroxyl group, a nitro group, an amino group, a carboxyl group, a carboxylic acid ester group, a nitrile group, or a combination thereof as a substituent.

[0056] (f) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), Ar 1 , and Ar 2 represents a benzene ring or a naphthalene ring, and R 1 and R 2 are each a substituent for a hydrogen atom on these rings and are selected from the group consisting of a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 3is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 4 is selected from the group consisting of aryl groups and heterocyclic groups having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R 5 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 4 and R 5 may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer of 0 to 3.

[0057] Preferably, R in the above formula (1) 5 is a hydrogen atom, and R 4 is an optionally substituted phenyl group, naphthyl group, anthryl group, or pyrenyl group. Preferably, R in the above formula (1) 3 is a hydrogen atom or a phenyl group. Preferably, in the unit structure (A), Ar 1 and Ar 2 contains a unit structure (a1) in which one of the units is a benzene ring and the other is a naphthalene ring. Preferably, in the unit structure (A), Ar 1 and Ar 2 Both of these contain a unit structure (a2) which is a benzene ring. A copolymer containing the unit structure (a1) and the unit structure (a2) is preferred.

[0058] Preferably, a unit structure (A) of formula (1) and a unit structure (B) of the following formula (2): [ka] (In formula (2), R 6 is selected from the group consisting of aryl groups and heterocyclic groups having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R 7 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 6 and R 7 may form a ring together with the carbon atoms to which they are attached. A copolymer containing the unit structure (a1) and the unit structure (B) is preferred.

[0059] (g) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), R 1 , R 2 , and R 3 are substituents for hydrogen atoms in the ring, and each independently represents a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond.4 R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond. 5 is a hydrogen atom, or a halogen atom, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms which may be substituted with a hydroxyl group, or a heterocyclic group; R 6 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, or a hydroxyl group, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, or R 5 and R 6 may form a ring together with the carbon atom to which they are attached. Ring A and ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring. n1, n2, and n3 each represent an integer of 0 or more up to the maximum number that can be substituted on the ring. Examples include polymers having a unit structure represented by the following formula:

[0060] Preferably, ring A and ring B are both benzene rings, n1, n2, and n3 are 0, and R 4 is a hydrogen atom. Preferably, R 5 is a hydrogen atom, or a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group which may be substituted with a hydroxyl group, a naphthyl group, an anthryl group, or a pyrenyl group, and R 6 is a hydrogen atom.

[0061] (h) Examples of the crosslinkable membrane material include those represented by the following formula (1a), formula (1b), and formula (1c), as disclosed in WO 2014 / 129582 A1: [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (1b), two R 3 and two R 4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (wherein two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are the same as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). represents a structural unit represented by the formula: Examples of the polymer include a polymer having one or more repeating structural units represented by the following formula:

[0062] Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0063] (i) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), R 1 ~R 4 Each of X independently represents a hydrogen atom or a methyl group. 1 represents a divalent organic group containing at least one arylene group which may be substituted with an alkyl group, an amino group, or a hydroxyl group.

[0064] Preferably, in formula (1), X 1 The arylene group in the definition is a phenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a pyrenylene group, or a carbazolylene group.

[0065] Preferably, in formula (1), X 1 is expressed as equation (2): [ka] [In formula (2), A 1 represents a phenylene group or a naphthylene group. 2 is a phenylene group, a naphthylene group, or a group of formula (3): [ka] (In formula (3), A 3 and A 4 each independently represents a phenylene group or a naphthylene group. A dotted line represents a bond. An organic group represented by the formula: ). A dotted line represents a bond. An organic group represented by the formula: ).

[0066] (j) Examples of crosslinkable film materials include novolak resins obtained by reacting an aromatic compound (A) with an aldehyde (B) having a formyl group bonded to a secondary or tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, as disclosed in WO 2017 / 069063 A1.

[0067] Preferably, the novolac resin is represented by the following formula (1): [ka] (In formula (1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, and b 1 represents an alkyl group having 1 to 16 carbon atoms; b 2 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0068] Preferably, A is a divalent group derived from an aromatic compound containing an amino group, a hydroxyl group, or both. Preferably, A is a divalent group derived from an aromatic compound, including an arylamine compound, a phenolic compound, or both. Preferably, A is a divalent group derived from aniline, diphenylamine, phenylnaphthylamine, hydroxydiphenylamine, carbazole, phenol, N,N'-diphenylethylenediamine, N,N'-diphenyl-1,4-phenylenediamine, or a polynuclear phenol. Preferably, the polynuclear phenol is dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 2,2'-biphenol, or 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

[0069] Preferably, the novolac resin is represented by the following formula (2): [ka] (In formula (2), a 1 and a 2 represents an optionally substituted benzene ring or naphthalene ring, and R 1 represents a secondary amino group or a tertiary amino group, a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an arylene group, or a divalent group to which any of these groups are optionally bonded. 3 represents an alkyl group having 1 to 16 carbon atoms; b 4 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0070] (k) Examples of the crosslinkable membrane material include those represented by the following formula (1a) and / or formula (1b): [ka] [In formulas (1a) and (1b), two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 each represent a phenyl group, they may be bonded to each other to form a fluorene ring, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, p represents an integer of 3 to 500, X represents a benzene ring, and the two -C(CH3)2- groups bonded to the benzene ring are in a meta or para position relationship. Examples of the polymer include a polymer having a repeating structural unit represented by the following formula:

[0071] Preferably, the polymer is a polymerization reaction product of at least one bisphenol compound and at least one aromatic aldehyde or aromatic ketone. Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0072] (l) Examples of cross-linkable membrane materials include poly(epoxide) resins having an epoxy functionality of greater than 2.0 and less than 10, such as those disclosed in JP-A-11-511194.

[0073] Preferably, the poly(epoxide) resin is selected from the group consisting of bisphenol A-epichlorohydrin resin products, epoxy novolacs, o-cresol epoxy novolacs, polyglycidyl ethers, polyglycidyl amines, cycloaliphatic epoxides, and polyglycidyl esters. Preferably, the poly(epoxide) resin has an epoxy functionality greater than 3.5.

[0074] (m) Examples of crosslinkable film materials or novolac film materials include compounds represented by the following formula (1) and novolac film materials, as disclosed in WO 2018 / 198960 A1. [ka] [In formula (1), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )- or -CH(R 1 )-, X 2 is -N(R 2 )- or -CH(R 2 )-, X 3 are -N=, -CH=, -N(R 3)- or -CH(R 3 )-, X 4 are -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1.]

[0075] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4is a hydroxy group or a C1-20 linear, branched or cyclic alkyl group which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom or a sulfur atom.

[0076] Preferably, the compound contains one or more units of one or more of repeating units a, b, c, d, e, f, g, h, and i represented by the following formula (2). [ka] [ka] Formula (2) [In formula (2), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )-, -CH(R 1 )-, -N< or -CH<; X 2 is -N(R 2 )-, -CH(R 2 )-, -N< or -CH<; X 3 are -N=, -CH=, -N(R 3 )-, -CH(R 3 )-, -N< or -CH<; X 4 are -N=, -CH=, -N(R 4 )-, -CH(R 4 )-, -N< or -CH<; R 1 , R 2 , R 3 and R 4are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; B 1 and B 2 are the same or different and each represents a group derived from an aromatic compound selected from the group consisting of a C1-20 linear, branched or cyclic alkyl group optionally interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, a C6-40 aryl group and a C6-40 heterocyclic group; B 1 and B 2 may form a ring together with the carbon atom to which they are bonded, and a hydrogen atom of the group derived from the aromatic compound may be substituted with a C1-20 alkyl group, a phenyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

[0077] Preferably, the compound contains one or more units of one or more of repeating units j, k, l, m, r, s, t, u, v, and w represented by the following formula (3). [ka] [ka] Formula (3) [In formula (3), [ka] represents a single bond or a double bond, X 1 represents -N< or -CH<, X 2 represents -N< or -CH<, X 3 are -N=, -CH=, -N(R 3 )- or -CH(R 3 )-, X 4 are -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9 and R 10are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; p and q are integers from 0 to 20, When the number of methylene groups is two or more, the number of methylene groups p and the number of methylene groups q may be interrupted by an oxygen atom or a sulfur atom. B 3 represents a direct bond or a group derived from a C6-40 aromatic compound which may be substituted with a C1-20 alkyl group, a phenyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

[0078] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4 is a hydroxy group or a C1-20 linear, branched or cyclic alkyl group which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom or a sulfur atom.

[0079] (n) Examples of crosslinkable film materials include epoxy adducts formed by reacting an epoxy group-containing compound having at least two epoxy groups with an epoxy adduct-forming compound having one epoxy addition reactive group, as disclosed in WO 2017 / 002653 A1. Examples of such epoxy adducts include the following.

[0080] [ka] [ka]

[0081] [ka]

[0082] [ka]

[0083] (In the formula, a, b, c, and d are each 0 or 1, and a+b+c+d=1.)

[0084] (o) Examples of the crosslinkable membrane material include those of formula (1):

[0085] [ka] (In the formula, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 represents a compound represented by formula (2), formula (3), formula (4), or formula (5):

[0086] [ka] (wherein R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; or R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms; R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms), and Q represents formula (6) or (7): [ka] (wherein Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group are each optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; and X2 represents formula (2), formula (3), or formula (5)).

[0087] Preferably, the structure represented by formula (1) is represented by formula (12): [ka] (wherein R1, R2, and Q have the same meanings as defined above) Or, equation (13): [ka] (wherein X1 has the same meaning as defined above, Y represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms, and m represents an integer of 0 to 4, and when m is 2 to 4, the Ys may be the same or different.) The structure is expressed as follows.

[0088] (p) Examples of the crosslinkable membrane material include those represented by formula (1) or (2): [ka] In the formula, R1 and R2 each represent a hydrogen atom, a methyl group, an ethyl group, or a halogen atom; A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group; and Q is a group represented by formula (3) or formula (4): [ka] [In the formula, Q1 represents an alkylene group having 1 to 15 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group are each optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; X1 represents a group represented by formula (5), (6), or formula (7): [ka] (wherein R3 and R4 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms, and R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R5 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms).)

[0089] Preferably, the polymer has the formula (12): [ka] (wherein Q has the same meaning as above)

[0090] Preferably, the polymer has formula (13) and formula (14): [ka] [Wherein Q2 is the formula (15), the formula (16) or the formula (17): [ka] (wherein Y, m, R3, R4 and R5 are as defined above), and Q3 represents a group represented by formula (18): [ka] (wherein Q4 represents an alkylene group having 1 to 15 carbon atoms, and n3 and n4 each represent the number 0 or 1.)

[0091] (q) Examples of the crosslinkable membrane material include those represented by the following formulas (1), (2), and (3): [ka] (In the above formula, X represents a hydrogen atom or an aromatic fused ring; Y represents an aromatic fused ring, and X and Y may be bonded to each other to form a fused ring; R1, R2, R3, R4, R5, R 10 , R 11 and R 12 each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, R6, R7, and R8 each represent a hydrogen atom or a linear or cyclic alkyl group having 1 to 10 carbon atoms; R9 represents a linear or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms; R7 and R8 may be bonded to each other to form a ring; M and Q each represent a direct bond or a linking group; and n represents an integer of 0 or 1.) or a combination of such polymers, wherein, when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) satisfy the following ranges: 0.3≦a≦0.95, 0.005≦b≦0.7, and 0≦c≦0.45.

[0092] Preferably, the polymer contains unit structures represented by formula (1) and formula (2), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (b) of unit structures represented by formula (2) satisfy the following conditions: 0.305≦a+b≦1, 0.3≦a≦0.95, 0.005≦b≦0.7. Preferably, the polymer contains unit structures represented by formula (1) and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (c) of unit structures represented by formula (3) are 0.35≦a+c≦1, 0.3≦a≦0.95, and 0.05≦c≦0.7. Preferably, the polymer contains unit structures represented by formula (1), formula (2), and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) satisfy the following conditions: 0.355≦a+b+c≦1, 0.3≦a≦0.9, 0.005≦b≦0.65, and 0.05≦c≦0.65. Preferably, the unit structure represented by formula (1) is a unit structure consisting of vinylnaphthalene, acenaphthylene, vinylanthracene, vinylcarbazole, or a derivative thereof. be.

[0093] (r) Examples of the crosslinkable membrane material include those of the following formula (2): [ka] (In formula (2), each of the two Ar represents an aryl group, the aryl group having at least one hydroxy group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond.) The molecular weight of the compound is, for example, 150 to 600.

[0094] In formula (2), examples of the aryl group represented by Ar include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. When Q represents a divalent linking group having at least one benzene ring or a naphthalene ring, examples of the divalent linking group include a divalent group in which at least one of the two hydrogen atoms of a methylene group is substituted with a phenyl group, a biphenylyl group, or a naphthyl group, a divalent aromatic group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and a divalent group having the divalent aromatic group and a methylene group, an ether group (-O- group), or a sulfide group (-S- group). Examples of the monomer include compounds represented by the following formulas (2-1) to (2-6). [ka] (In formula (2-6), m represents an integer of 0 to 3.)

[0095] (s) Examples of the film material capable of crosslinking include those having a structure in which one fullerene molecule is reacted with a compound represented by the following formula (1): [ka] (In the formula, each R independently represents an alkyl group having 1 to 10 carbon atoms.) Examples of the fullerene derivative include a fullerene derivative having one to six molecules of malonic acid diester added thereto, which is represented by the following formula:

[0096] (t) Examples of the crosslinkable membrane material include polyfunctional (meth)acrylate compounds having a molecular weight of 300 to 10,000 that are in a liquid state at room temperature and atmospheric pressure, as disclosed in WO 2011 / 132640 A1.

[0097] Preferably, the compound has 2 to 20 (meth)acrylate groups in the molecule. Preferably, the molecular weight of the compound is between 300 and 2,300.

[0098] Examples of such compounds include the following:

[0099] [ka]

[0100] [ka]

[0101] (u) Examples of membrane materials capable of crosslinking include compound (E) containing partial structure (I) and partial structure (II), as disclosed in WO 2017 / 154921 A1, in which partial structure (II) contains a hydroxy group generated by the reaction of an epoxy group with a proton-generating compound, partial structure (I) is at least one partial structure selected from the group consisting of partial structures represented by formulas (1-1) to (1-5) below, or a partial structure consisting of a combination of a partial structure represented by formula (1-6) and a partial structure represented by formula (1-7) or formula (1-8), and partial structure (II) is a partial structure represented by formula (2-1) or formula (2-2) below. [ka] (In the formula, R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , and R 6each represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , R 6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5 represents a trivalent group, and R 7 , R 8 , R 9 , R 10 and R 11 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, n represents the number of repeating units from 1 to 10, and dotted lines represent chemical bonds with adjacent atoms.

[0102] Preferably, compound (E) contains epoxy groups and hydroxy groups in a molar ratio of 0≦(epoxy groups) / (hydroxy groups)≦0.5, and contains partial structure (II) in a molar ratio of 0.01≦(partial structure (II)) / (partial structure (I)+partial structure (II))≦0.8. Preferably, compound (E) is a compound containing at least one partial structure (I) and at least one partial structure (II). Preferably, the above R 5a , and R 6a are each a divalent group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, or a combination thereof. Preferably, compound (E) contains 1 to 1000 of each of partial structure (I) and partial structure (II).

[0103] (v) Examples of crosslinkable film materials include compounds containing at least one photodegradable nitrogen-containing structure and / or photodegradable sulfur-containing structure and a hydrocarbon structure, as disclosed in WO 2018 / 030198 A1.

[0104] Preferably, the compound is a compound having one or more photodegradable nitrogen-containing structures and / or photodegradable sulfur-containing structures in the molecule. Preferably, the compound is a compound in which a photodegradable nitrogen-containing structure and / or a photodegradable sulfur-containing structure and a hydrocarbon structure are present in the same molecule, or a combination of compounds in which the structures are present in different molecules. Preferably, the hydrocarbon structure is a saturated or unsaturated group having 1 to 40 carbon atoms, and is a linear, branched, or cyclic hydrocarbon group. Preferably, the photodecomposable nitrogen-containing structure is a structure that generates a reactive nitrogen-containing functional group or a reactive carbon-containing functional group upon irradiation with ultraviolet light, or a structure that contains a reactive nitrogen-containing functional group or a reactive carbon-containing functional group generated upon irradiation with ultraviolet light. Preferably, the photodecomposable nitrogen-containing structure is a photodecomposable nitrogen-containing structure which may contain a sulfur atom, and the structure is an azide structure, a tetraazole structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, a diazo structure, or a structure containing a combination thereof. Preferably, the photodecomposable sulfur-containing structure is a structure that generates an organic sulfur radical or a carbon radical upon irradiation with ultraviolet light, or a structure that contains an organic sulfur radical or a carbon radical generated upon irradiation with ultraviolet light. Preferably, the photodecomposable sulfur-containing structure is a photodecomposable sulfur-containing structure which may contain a nitrogen atom, and the structure is a trisulfide structure, a disulfide structure, a sulfide structure, a thioketone structure, a thiophene structure, a thiol structure, or a structure containing a combination thereof.

[0105] Preferred are the following compounds: [ka] [ka]

[0106] (w) Examples of the crosslinkable membrane material include compounds represented by the following formula (1), as disclosed in WO 2019 / 013293 A1: [ka] (In formula (1), R 1 are each independently a divalent group having 1 to 30 carbon atoms, and R 2 ~R 7 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group, and R 5 At least one of m is a hydroxyl group or a thiol group, 2 , m 3 and m 6 are each independently an integer of 0 to 9, and m 4 and m 7 are each independently an integer of 0 to 8, and m 5 is an integer from 1 to 9, n is an integer from 0 to 4, and p 2 ~p 7 are each independently an integer of 0 to 2.

[0107] Preferred are the following compounds: [ka]

[0108] (x) Examples of a film material capable of undergoing a crosslinking reaction include compounds represented by the following general formula (1), as disclosed in JP-A-2016-216367: [ka] (In the formula, n1 and n2 each independently represent 0 or 1, W is a single bond or any of the structures represented by the following formula (2), R1 is any of the structures represented by the following general formula (3), and m1 and m2 each independently represent an integer of 0 to 7, with the proviso that m1+m2 is 1 or more and 14 or less.) [ka] (In the formula, l represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to the aromatic ring, and Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, anthracenyl group, or pyrenyl group. When Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group.)

[0109] Preferably, the compound represented by the general formula (1) is a compound represented by the following general formula (4). [ka] (In the formula, m3 and m4 represent 1 or 2, and W and R1 are the same as above.)

[0110] Preferably, the W is a single bond or a structure represented by the following formula (5). [ka] (wherein l is the same as above).

[0111] Preferably, the compound represented by the general formula (1) has two or more Q1s in the molecule, and the Q1s include one or more types of structures represented by the following general formula (6) and one or more types of structures represented by the following general formula (7). [ka] (wherein ** represents the bonding site to the carbonyl group, R h represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R h The methylene group constituting the formula (I) may be substituted with an oxygen atom or a carbonyl group. [ka] (wherein ** represents the bonding site to the carbonyl group, R i represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2.

[0112] (y) Examples of a film material capable of undergoing a crosslinking reaction include compounds represented by the following general formula (1A), as disclosed in JP-A-2017-119670. [ka] (In the formula, R represents a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group; R1 represents a group represented by the following general formula (1B); and m1 and m2 represent integers satisfying 1 ≦ m1 ≦ 5, 1 ≦ m2 ≦ 5, and 2 ≦ m1 + m2 ≦ 8.) [ka] (In the formula, X 1 is a group represented by the following general formula (1C), and X is a group represented by the following general formula (1D). [ka] (In the formula, (X) represents the bonding site to the X.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (1E), and n5 is 0, 1, or 2. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group.

[0113] Preferably, the molecular weight of the compound is 2,500 or less.

[0114] Preferred are compounds represented by the following general formula (2A) and compounds represented by the following general formula (3A). [ka] (In the formula, R represents a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group; R2 represents a group represented by the following general formula (2B); and m3 and m4 represent integers satisfying 1 ≦ m3 ≦ 5, 1 ≦ m4 ≦ 5, and 2 ≦ m3 + m4 ≦ 8.) [ka] (In the formula, X 11 is a group represented by the following general formula (2C), and X' is a group represented by the following general formula (2D). [ka] (In the formula, (X') represents the bonding site to the X'.) [ka] (wherein n3 is 0 or 1, n4 is 1 or 2, and X 4 is a group represented by the following general formula (2E), and n6 is 0, 1, or 2. [ka] (In the formula, R 11 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. [ka] (In the formula, R 101 , R 102 , R 103 , R 104 are each independently a hydroxyl group, m100 is 1, 2, or 3, and R 100 represents a hydrogen atom or a hydroxyl group when m100 is 1, a single bond or a group represented by the following general formula (3B) when m100 is 2, and a group represented by the following general formula (3C) when m100 is 3, wherein the hydrogen atom on the aromatic ring may be substituted with a methyl group or a methoxy group. m101 is 0 or 1, m102 is 1 or 2, m103 is 0 or 1, m104 is 1 or 2, and m105 is 0 or 1. When m101 is 0, n101 and n102 are integers that satisfy 0≦n101≦3, 0≦n102≦3, and 1≦n101+n102≦4, and when m101 is 1, n101, n102, n103, and n104 are integers that satisfy 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and 2≦n101+n102+n103+n104≦8. [ka] (where * indicates a bonding position, and R 106 , R 107is a hydrogen atom or an organic group having 1 to 24 carbon atoms and not containing an ester bond, and R 106 and R 107 may be bonded to form a cyclic structure. [ka] (where * indicates a bonding position, and R 108 is a hydrogen atom or an organic group having 1 to 15 carbon atoms.

[0115] (z) Examples of polyether membrane materials include polymers represented by the following general formula (1), as disclosed in WO2012 / 050064. The following formula (1): [ka] (in formula (1), Ar1 represents an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms), a unit structure represented by the following formula (2): [ka] (wherein in formula (2), Ar2, Ar3, and Ar4 each represent an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group), or a polymer containing a combination of a unit structure represented by formula (1) and a unit structure represented by formula (2).

[0116] The crosslinkable membrane material (B) is preferably (B1) a membrane material containing an aliphatic ring (e.g., (a)(m) above); (B2) Novolak film materials (e.g., (b)(c)(d)(e)(f)(g)(h)(i)(j)(k)(l) above), (B3) polyether membrane materials (e.g., (z) above); (B4) polyester film materials (e.g., (o) and (p) above); (B5) a compound different from the crosslinkable compound (A) (for example, the above (m), (n), (r), (s), (t), (u), (v), (w), (x), and (y)), (B6) a membrane material containing an aromatic fused ring (e.g., (q) above); (B7) acrylic resin, and (B8) methacrylic resin The compound includes at least one selected from the group consisting of:

[0117] When the resist underlayer film-forming composition of the present invention contains a crosslinkable film material (B) (a film material or a polymer), the content of the crosslinkable film material (B) is usually 1 to 99.9 mass%, preferably 50 to 99.9 mass%, more preferably 50 to 95 mass%, and even more preferably 50 to 90 mass%, based on the total solid content.

[0118] [(C) Acid catalyst] The acid catalyst optionally contained in the resist underlayer film-forming composition according to the present invention is not particularly limited as long as it is a catalyst that can promote the reaction between the above-mentioned crosslinking compound (A) and the crosslinkable film material (B).

[0119] Examples of acid catalysts include sulfonic acid compounds and carboxylic acid compounds such as pyridinium p-toluenesulfonate, pyridinium p-hydroxybenzenesulfonate, pyridinium trifluoromethanesulfonate, p-toluenesulfonic acid, p-hydroxybenzenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, chlorobenzenesulfonic acid, methyl 4-phenolsulfonate, benzenesulfonic acid, naphthalenesulfonic acid, citric acid, and benzoic acid; and thermal acid generators such as K-PURE (registered trademark) TAG2689, TAG2690, TAG2678, and CXC-1614 (all manufactured by King Industries), which are quaternary ammonium salts of trifluoromethanesulfonic acid; 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters. These acid catalysts may be contained alone or in combination of two or more. Among the acid catalysts, pyridinium p-hydroxybenzenesulfonate is preferred.

[0120] A catalyst ion exchange resin can be used to prevent unreacted acid, catalyst, deactivated catalyst, etc. from remaining in the reaction system. For example, a strong acid ion exchange resin such as a sulfonic acid type can be used as the catalyst ion exchange resin.

[0121] When the resist underlayer film forming composition according to the present invention contains an acid catalyst, the acid catalyst is contained in an amount of, for example, 1% by mass to 30% by mass, preferably 5% by mass to 15% by mass, relative to the content of the crosslinking agent.

[0122] (D) Solvent In the resist underlayer film-forming composition according to the present invention, the solvent for dissolving the above-mentioned crosslinking compound (A), as well as the optional crosslinkable film material (B), acid catalyst (C), and other components is not particularly limited as long as it is a solvent that can dissolve these components uniformly.

[0123] For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexanone, butanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0124] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Reusing the solvent used for preparing the crosslinkable compound (A) or the crosslinkable membrane material (B) as a solvent as is contributes to the effective use of resources and is advantageous.

[0125] These solvents may also be mixed with high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0126] The amount of solvent is selected so that the solids content of the resist underlayer film-forming composition according to the present invention is preferably 0.1 to 70 mass %, more preferably 0.1 to 60 mass %, where the solids content refers to the content of all components in the resist underlayer film-forming composition excluding the solvent.

[0127] [Other ingredients] In addition to the above, surfactants, rheology modifiers, adhesion aids, light absorbing agents, etc. may be added to the resist underlayer film forming composition according to the present invention, if necessary.

[0128] The resist underlayer film-forming composition of the present invention may contain a surfactant as an optional component to improve its coatability on semiconductor substrates. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; F-Top (registered trademark) EF301, EF303, and EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Megafac (registered trademark) F171, F173, R-30, R-30N, R-40, and R-40-LM (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); , manufactured by DIC Corporation), Fluorad FC430, FC431 (all manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (all manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. The blending amount of these surfactants is usually 2.0 mass % or less, preferably 1.0 mass % or less, based on the total solids content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0129] Rheology modifiers are added primarily to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically added in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0130] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion promoter include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion promoters are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition for lithography.

[0131] Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbent is typically blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solid content of the resist underlayer film-forming composition.

[0132] The resist underlayer film-forming composition according to the present invention may also contain a crosslinking agent other than the crosslinking compound represented by formula (I). Examples of such crosslinking agents include melamine-based agents, substituted urea-based agents, and polymers thereof. A crosslinking agent having at least two crosslink-forming substituents is preferred, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0133] The resist underlayer film-forming composition according to the present invention can be prepared by uniformly mixing the above-mentioned components by a conventional method. The prepared resist underlayer film-forming composition is preferably used after filtering using a filter having a pore size of, for example, 0.2 μm or 0.1 μm and / or a filter having a pore size of 0.01 μm.

[0134] [Method for manufacturing patterned substrate] A method for producing a patterned substrate using the resist underlayer film-forming composition according to the present invention includes the steps of applying the resist underlayer film-forming composition onto a semiconductor substrate and curing it to form a resist underlayer film, applying a resist onto the resist underlayer film and baking it to form a resist film, exposing the resist underlayer film and the semiconductor substrate coated with the resist to light, and developing and patterning the exposed resist film. Each step will be described in order below.

[0135] Examples of semiconductor substrates onto which the resist underlayer film-forming composition of the present invention can be applied include silicon substrates, germanium substrates, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0136] The resist underlayer film-forming composition according to the present invention is applied onto such a semiconductor substrate by an appropriate application method such as a spinner, a coater, etc. The coating film is then cured to form the resist underlayer film according to the present invention, which is a cured product of the coating film. The means for curing the coating film include baking the coating film using a heating means such as a hot plate, and photo-curing the coating film by irradiating it with light (for example, ultraviolet light). Baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 to 30 minutes, more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 to 10 minutes, and most preferably, the baking temperature is 200°C to 260°C and the baking time is 0.8 to 3 minutes. The thickness of the resist underlayer film formed is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, and most preferably 0.02 to 0.3 μm. If the baking temperature is lower than the above range, crosslinking may be insufficient, and the formed resist underlayer film may not be resistant to resist solvents or aqueous hydrogen peroxide solutions. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may be thermally decomposed. When the coating film is cured by baking alone, the resist underlayer film according to the present invention is a baked product of the coating film.

[0137] Instead of curing the coating film by baking alone, the coating film can be heat-treated at a relatively low temperature (e.g., 10 to 80°C lower than the above-mentioned bake temperature) and then photo-cured to complete the curing. Alternatively, the coating film can be heat-treated for a shorter time at the above-mentioned bake temperature and then photo-cured to complete the curing. For the photo-curing treatment, ultraviolet light is preferably used. The irradiation energy is usually 100 to 1,000 mJ / cm. 2 is. By appropriately combining thermal curing and photocuring, the planarization properties of the resist underlayer film can be further improved.

[0138] Next, a resist pattern is formed on the resist underlayer film. The resist pattern can be formed by a general method, i.e., by applying a photoresist solution onto the resist underlayer film (after forming one to several layers of coating material as needed), pre-baking (if necessary), irradiating (exposure) with light or electron beams through a predetermined mask, post-exposure baking (PEB) (if necessary), developing, rinsing, and drying. The resist used in the present invention is a photoresist or electron beam resist. The photoresist solution used to form the resist pattern is not particularly limited as long as it is sensitive to the light used for exposure, and a positive photoresist can be used. Examples of the photoresist include chemically amplified photoresists consisting of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low molecular compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and photoresists consisting of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and an acid-soluble binder. Examples of such photoresists include chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes to increase the alkaline dissolution rate of the photoresist and a photoacid generator, and DNQ-novolac non-chemically amplified photoresists that utilize the difference in alkaline dissolution rate between exposed and unexposed areas. Examples include PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), TDUR-P3435LP and THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Negative photoresists can also be used instead of positive photoresists.

[0139] Examples of the electron beam resist to be applied on top of the resist underlayer film in the present invention include a composition comprising a resin containing a Si-Si bond in the main chain and an aromatic ring at the terminal, and an acid generator that generates acid upon irradiation with an electron beam, or a composition comprising poly(p-hydroxystyrene) in which the hydroxyl group is substituted with an organic group containing N-carboxyamine, and an acid generator that generates acid upon irradiation with an electron beam. In the latter electron beam resist composition, the acid generated from the acid generator upon irradiation with an electron beam reacts with the N-carboxyaminooxy group in the polymer side chain, decomposing the polymer side chain into a hydroxyl group, making it alkali-soluble and dissolving in an alkaline developer, thereby forming a resist pattern. Acid generators that generate acid upon irradiation with an electron beam include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0140] The exposure is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. An alkaline developer is used for the development, with the development temperature appropriately selected from 5°C to 50°C and the development time appropriately selected from 10 seconds to 300 seconds. Examples of the alkaline developer include aqueous alkaline solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Instead of an alkaline developer, development can also be carried out with an organic solvent such as butyl acetate to develop portions of the photoresist where the alkaline dissolution rate is not improved.

[0141] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask, to expose the surface of the inorganic film if the inorganic film is formed on the surface of the semiconductor substrate used, or to expose the surface of the semiconductor substrate if the inorganic film is not formed on the surface of the semiconductor substrate used.

[0142] Furthermore, a desired pattern can be formed by wet etching using an aqueous hydrogen peroxide solution, using the resist underlayer film after dry etching (and the resist pattern, if any, remaining on the resist underlayer film) as a mask. Examples of wet etching chemicals include basic hydrogen peroxide solutions obtained by mixing a basic substance, such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or an organic amine such as triethanolamine, with hydrogen peroxide to achieve a basic pH, and acidic hydrogen peroxide solutions obtained by mixing an inorganic acid, such as hydrochloric acid or sulfuric acid, with hydrogen peroxide. Other wet etching chemicals that can achieve a basic pH include those obtained by mixing urea with hydrogen peroxide and heating the mixture to generate ammonia through thermal decomposition of the urea, ultimately achieving a basic pH. The temperature at which the basic hydrogen peroxide solution and the acidic hydrogen peroxide solution are used is preferably 25°C to 90°C, and more preferably 40°C to 80°C. The wet etching time is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes.

[0143] As described above, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate from the resist underlayer film-forming composition, forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the underlayer film using the resist pattern, and processing a semiconductor substrate with the patterned underlayer film. [Example]

[0144] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these.

[0145] The chemical structures and abbreviations of the raw materials used in the synthesis examples are as follows: [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0146] The chemical structures (examples) and abbreviations of the raw materials used in the synthesis examples are as follows: [ka] (In the above formula, m represents an integer of 0 to 3.) [ka] [ka]

[0147] The weight average molecular weight of the resin (polymer) obtained in the following Synthesis Example 1 is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). For the measurement, a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions etc. are as follows. GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40℃ Solvent: tetrahydrofuran (THF) Flow rate: 1.0ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0148] [Synthesis Example 1] A 100 mL two-neck flask was charged with 10.90 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 10.00 g of 2-ethylhexyl glycidyl ether (Tokyo Chemical Industry Co., Ltd.), 1.03 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 21.0 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 21.0 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 21.0 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-1) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 960, and no residual epoxy was present. [ka]

[0149] [Synthesis Example 2] A 100 mL two-neck flask was charged with 9.80 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 12.00 g of 2-biphenyl glycidyl ether (Tokyo Chemical Industry Co., Ltd.), 1.00 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 22.8 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 22.8 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 22.8 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-2) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 680, and no residual epoxy was present. [ka]

[0150] [Synthesis Example 3] A 100 mL two-neck flask was charged with 9.60 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 12.00 g of glycidyl 4-tert-butylbenzoate (Tokyo Chemical Industry Co., Ltd.), 0.98 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 22.6 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 22.6 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 22.6 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-3) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 870, and no residual epoxy was present. [ka]

[0151] [Synthesis Example 4] A 100 mL two-neck flask was charged with 3.34 g of HMOM-TPPA (Honshu Chemical Industry Co., Ltd.), 3.00 g of 2-ethylhexyl glycidyl ether (Tokyo Chemical Industry Co., Ltd.), 0.31 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 15.5 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 6.6 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 6.6 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-4) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,200, and no residual epoxy was present. [ka]

[0152] [Synthesis Example 5] A 100 mL two-neck flask was charged with 9.62 g of TM-BIP-A (Asahi Organic Chemicals Co., Ltd.), 10.00 g of 2-ethylhexyl glycidyl ether (Tokyo Chemical Industry Co., Ltd.), 1.03 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 48.2 g of propylene glycol monomethyl ether. The mixture was then heated to 80 °C and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 20.6 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 20.6 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-5) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,600, and the residual epoxy was 2.5% based on the amount charged. [ka]

[0153] [Synthesis Example 6] A 100 mL two-neck flask was charged with 7.87 g of TM-BIP-A (Asahi Organic Chemicals Co., Ltd.), 10.00 g of 2-biphenyl glycidyl ether (Tokyo Chemical Industry Co., Ltd.), 0.84 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 43.7 g of propylene glycol monomethyl ether. The mixture was then heated to 80 °C and stirred for approximately 21 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 18.7 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 18.7 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-6) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 900, and the residual epoxy was 0.2% based on the amount charged. [ka]

[0154] [Synthesis Example 7] A 100 mL two-neck flask was charged with 7.68 g of TM-BIP-A (Asahi Organic Chemicals Co., Ltd.), 10.00 g of glycidyl 4-tert-butylbenzoate (Tokyo Chemical Industry Co., Ltd.), 0.82 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 43.2 g of propylene glycol monomethyl ether. The mixture was then heated to 80 °C and stirred for approximately 21 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 18.5 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 18.5 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-7) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,700, and the residual epoxy was 1.1% based on the amount charged. [ka]

[0155] [Synthesis Example 8] A 100 mL two-neck flask was charged with 7.89 g of 2,6-bis(hydroxymethyl)-p-cresol (Tokyo Chemical Industry Co., Ltd.), 10.00 g of RE-810 NM (Nippon Kayaku Co., Ltd.), 0.87 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 8.42 g of propylene glycol monomethyl ether. The mixture was then heated to 100 °C and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 18.8 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 18.8 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-8) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,900, and no residual epoxy was present. [ka]

[0156] [Synthesis Example 9] A 100 mL two-neck flask was charged with 9.09 g of 2,6-bis(hydroxymethyl)-p-cresol (Tokyo Chemical Industry Co., Ltd.), 10.00 g of YX-4000 (Mitsubishi Chemical Corporation), 1.00 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 8.61 g of propylene glycol monomethyl ether. The mixture was then heated to 100 °C and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 20.1 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 20.1 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-9) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,500, and no residual epoxy was present. [ka]

[0157] [Synthesis Example 10] A 100 mL two-neck flask was charged with 6.89 g of 2,6-bis(hydroxymethyl)-p-cresol (Tokyo Chemical Industry Co., Ltd.), 10.00 g of HP-6000 (DIC Corporation), 0.76 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 7.57 g of propylene glycol monomethyl ether. The mixture was then heated to 100 °C and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether, and 17.7 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 17.7 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, followed by ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplary) of formula (1-10) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,900, and no residual epoxy was present. [ka] (In formula (1-10), s represents an integer of 0 to 3.)

[0158] [Synthesis Example 11] A 100 mL two-neck flask was charged with 7.20 g of 2,6-bis(hydroxymethyl)-p-cresol (Tokyo Chemical Industry Co., Ltd.), 10.00 g of NC-7300L (Nippon Kayaku Co., Ltd.), 0.80 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 7.71 g of propylene glycol monomethyl ether. The mixture was then heated to 100 °C and stirred for approximately 24 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 18.0 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 18.0 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplary) of formula (1-11) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,200, and no residual epoxy was present. [ka]

[0159] [Synthesis Example 12] A polymer was obtained by the method described in Synthesis Example 10 of Japanese Patent No. 6191831. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000.

[0160] [Synthesis Example 13] A 100 mL two-neck flask was charged with 8.74 g of 3,7-dihydroxy-2-naphthoic acid, 10.00 g of NC-7300L (Nippon Kayaku Co., Ltd.), 0.40 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 44.7 g of propylene glycol monomethyl ether. The mixture was then heated to 120 °C and stirred for approximately 18 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 19.4 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 19.4 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplary) of formula (1-13) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,100, and no residual epoxy was found. [ka]

[0161] [Example 1] The polymer obtained in Synthesis Example 12 was dissolved in propylene glycol monomethyl ether acetate, and an anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and a cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added thereto, followed by ion exchange treatment at room temperature for 4 hours to obtain a polymer solution (solid content: 34.3% by mass). To 2.6 g of this polymer solution, 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.1 g of a solution of the compound obtained in Synthesis Example 1 (solid content: 24.2% by mass), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 1.3 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0162] [Example 2] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.0 g of a solution of the compound obtained in Synthesis Example 2 (solid content: 26.1% by mass), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 1.3 g of propylene glycol monomethyl ether were added to 2.6 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0163] [Example 3] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.0 g of a solution of the compound obtained in Synthesis Example 3 (solid content: 26.5% by mass), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 1.3 g of propylene glycol monomethyl ether were added to 2.6 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0164] [Example 4] A solution (solid content 29.1% by mass) of the polymer obtained in Synthesis Example 13 was obtained in the same manner as in Example 1. 0.16 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.0 g of a solution of the compound obtained in Synthesis Example 1 (solid content 24.2% by mass), 1.8 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.0 g of propylene glycol monomethyl ether acetate, and 5.4 g of propylene glycol monomethyl ether were added to 2.7 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0165] [Example 5] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.4 g of a solution of the compound obtained in Synthesis Example 8 (solid content: 24.1% by mass), 2.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.1 g of propylene glycol monomethyl ether acetate, and 0.6 g of propylene glycol monomethyl ether were added to 2.4 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0166] [Example 6] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.5 g of a solution of the compound obtained in Synthesis Example 9 (solid content: 22.0% by mass), 2.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.1 g of propylene glycol monomethyl ether acetate, and 0.5 g of propylene glycol monomethyl ether were added to 2.4 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0167] [Example 7] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.3 g of a solution of the compound obtained in Synthesis Example 10 (solid content: 24.5% by mass), 2.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.1 g of propylene glycol monomethyl ether acetate, and 0.7 g of propylene glycol monomethyl ether were added to 2.4 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0168] [Example 8] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.2 g of a solution of the compound obtained in Synthesis Example 11 (solid content: 27.1% by mass), 2.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.1 g of propylene glycol monomethyl ether acetate, and 0.8 g of propylene glycol monomethyl ether were added to 2.4 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0169] [Example 9] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.0 g of a solution of the compound obtained in Synthesis Example 4 (solid content: 26.9% by mass), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 1.4 g of propylene glycol monomethyl ether were added to 2.6 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0170] [Example 10] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.95 g of a solution of the compound obtained in Synthesis Example 5 (solid content: 20.6% by mass), 1.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.8 g of propylene glycol monomethyl ether acetate, and 1.9 g of propylene glycol monomethyl ether were added to 2.8 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0171] [Example 11] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.82 g of a solution of the compound obtained in Synthesis Example 6 (solid content: 23.9% by mass), 1.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.8 g of propylene glycol monomethyl ether acetate, and 2.0 g of propylene glycol monomethyl ether were added to 2.8 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0172] [Example 12] A solution (solid content: 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFACE R-40, manufactured by DIC Corporation), 0.83 g of a solution of the compound obtained in Synthesis Example 7 (solid content: 23.5% by mass), 1.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.8 g of propylene glycol monomethyl ether acetate, and 2.0 g of propylene glycol monomethyl ether were added to 2.8 g of this polymer solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0173] [Comparative Example 1] The polymer obtained in Synthesis Example 12 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a polymer solution (solid content: 34.3% by mass). 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.27 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 2.1 g of propylene glycol monomethyl ether were added to 2.6 g of this polymer solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0174] Comparative Example 2 A solution (solid content 29.1% by mass) of the polymer obtained in Synthesis Example 13 was obtained by the same method as in Example 1. 0.16 g of propylene glycol monomethyl ether acetate containing 1% of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.23 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.8 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.0 g of propylene glycol monomethyl ether acetate, and 6.2 g of propylene glycol monomethyl ether were added to and dissolved in 2.7 g of this polymer solution, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0175] Comparative Example 3 A solution (solid content 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.12 g of propylene glycol monomethyl ether acetate containing 1% of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.49 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.5 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 10.4 g of propylene glycol monomethyl ether acetate, and 3.9 g of propylene glycol monomethyl ether were added to and dissolved in 3.6 g of this polymer solution, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0176] Comparative Example 4 A solution (solid content 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFACE R-40, manufactured by DIC Corporation), 0.27 g of HMOM-TPPA (manufactured by Honshu Chemical Industry Co., Ltd.), 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 2.1 g of propylene glycol monomethyl ether were added to and dissolved in 2.6 g of this polymer solution, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0177] Comparative Example 5 A solution (solid content 34.3% by mass) of the polymer obtained in Synthesis Example 12 was obtained in the same manner as in Example 1. 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.20 g of TM-BIP-A (manufactured by Asahi Organic Chemicals Co., Ltd.), 1.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.8 g of propylene glycol monomethyl ether acetate, and 2.6 g of propylene glycol monomethyl ether were added to and dissolved in 2.8 g of this polymer solution, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0178] (Test for elution into resist solvent) The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-5 and Examples 1-12 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 240°C for 60 seconds to form resist underlayer films (film thickness 0.20 µm). These resist underlayer films were immersed in solvents used in resists: ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. These resist underlayer films were insoluble in these solvents.

[0179] (Optical constant measurement) The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-5 and Examples 1-12 were each applied to a silicon wafer using a spin coater. The resist underlayer films were baked on a hot plate at 240°C for 60 seconds to form resist underlayer films (film thickness 0.05 μm). The refractive index (n value) and optical absorption coefficient (k value, also called extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Tables 1-5.

[0180] [Table 1]

[0181] [Table 2]

[0182] [Table 3]

[0183] [Table 4]

[0184] [Table 5]

[0185] [Dry etching rate measurement] The etcher and etching gas used in measuring the dry etching rate were as follows: RIE-10NR (Samco): CF4 The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-5 and Examples 1-12 were each applied to a silicon wafer using a spin coater. The resist underlayer film (film thickness: 0.20 μm) was formed by baking on a hot plate at 240°C for 60 seconds. The dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rate ratios for Comparative Examples 1-5 and Examples 1-12 were calculated. The dry etching rate ratios were the dry etching rate ratios of (resist underlayer film) / (KrF photoresist). The results are shown in Tables 6-10.

[0186] [Table 6]

[0187] [Table 7]

[0188] [Table 8]

[0189] [Table 9]

[0190] [Table 10]

[0191] (Embeddability evaluation) The embedding ability was confirmed in a dense pattern area of ​​a 200 nm thick SiO2 substrate with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Examples 1-5 and Examples 1-12 were applied to the substrate and baked at 240°C for 60 seconds to form resist underlayer films of approximately 200 nm. The cross-sectional shape of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation to confirm whether the resist underlayer film-forming composition had filled the interior of the pattern. The results are shown in Tables 11-15. The embedding ability was evaluated as good ("◯") when the resist underlayer film was formed without gaps within the pattern, and poor ("×") when it was not embedded within the pattern or holes or gaps were present within the pattern.

[0192] [Table 11]

[0193] [Table 12]

[0194] [Table 13]

[0195] [Table 14]

[0196] [Table 15]

[0197] The crosslinking agents used in Examples 1-12 exhibit good embedding properties similar to conventional crosslinking agents.

[0198] (Coating test on uneven substrate) In a coating test for a stepped substrate, a comparison was made of the coating thickness between a dense area (DENSE) with a trench width of 50 nm and a pitch of 100 nm on a 200 nm SiO2 substrate and an open area (OPEN) without a pattern. The resist underlayer film-forming compositions prepared in Comparative Examples 1-5 and Examples 1-11 were applied to the substrate and baked at 240°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of the substrate was evaluated by observing the film thickness difference between the trench area (patterned area) and the open area (non-patterned area) of the stepped substrate (the coating step between the trench area and the open area, referred to as bias). Here, planarization refers to a small difference in film thickness (iso-dense bias) between the patterned area (dense area (patterned area)) and the non-patterned area (open area (non-patterned area)). The results are shown in Tables 16 to 20. In comparison with the comparative example (control) which was rated △, examples in which improvement (reduction of less than 15 nm) was confirmed were rated ○, and examples in which significant improvement (reduction of 15 nm or more) was confirmed were rated ⊚.

[0199] [Table 16]

[0200] [Table 17]

[0201] [Table 18]

[0202] [Table 19]

[0203] [Table 20]

[0204] It was confirmed that Examples 1-12 had improved planarization properties compared to the comparative examples.

[0205] [Synthesis Example 21] A 100 mL two-neck flask was charged with 19.12 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 15.00 g of RE810-NM (Nippon Kayaku Co., Ltd.), 0.65 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 81.14 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 14 hours. After the reaction was completed, 34.8 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 34.8 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-21) was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 6,000. [ka]

[0206] [Synthesis Example 22] A 100 mL two-neck flask was charged with 26.96 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 10.00 g of 1,4-butanediol diglycidyl ether (Tokyo Chemical Industry Co., Ltd.), 0.92 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 56.8 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 14.5 hours. After the reaction was complete, the mixture was diluted with propylene glycol monomethyl ether. 37.9 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 37.9 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-22) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,800. [ka]

[0207] [Synthesis Example 23] A 100 mL two-neck flask was charged with 17.45 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 15.00 g of HP-6000 (DIC Corporation), 0.60 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 77.1 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, 33.0 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 33.0 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-23) was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 10,500. [ka]

[0208] [Synthesis Example 24] A 100 mL two-neck flask was charged with 22.0 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 15.00 g of YX-4000 (Mitsubishi Chemical Corporation), 0.75 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 88.1 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, 37.8 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 37.8 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-24) was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,200. [ka]

[0209] [Synthesis Example 25] A 100 mL two-neck flask was charged with 17.5 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 15.00 g of 9,9-bis(4-glycidyloxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 0.60 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 77.2 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, 33.1 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 33.1 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-25) was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 5,200. [ka]

[0210] [Synthesis Example 26] A 100 mL two-neck flask was charged with 25.7 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 15.00 g of 4-cyclohexene-1,2-dicarboxylate diglycidyl (Tokyo Chemical Industry Co., Ltd.), 0.89 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 97.0 g of propylene glycol monomethyl ether. The mixture was then heated to 140 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, 41.6 g of anion exchange resin (Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 41.6 g of cation exchange resin (Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, compound solution (1-26) was obtained. The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,900. [ka]

[0211] [Synthesis Example 27] A polymer was obtained by the method described in Synthesis Example 10 of Japanese Patent No. 6,191,831. The weight-average molecular weight Mw measured by GPC in terms of polystyrene was 2,000. The obtained polymer was dissolved in propylene glycol monomethyl ether acetate, and an anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and a cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added, followed by ion exchange treatment at room temperature for 4 hours to obtain a compound solution (1-27).

[0212] [Synthesis Example 28] A 100 mL two-neck flask was charged with 72.46 g of propylene glycol monomethyl ether, 26.00 g of RE810-NM (Nippon Kayaku Co., Ltd.), 20.81 g of BPA-CA (Konishi Chemical Co., Ltd.), 2.18 g of ethyltriphenylphosphonium bromide, and 0.32 g of hydroquinone. The mixture was then reacted at 140 °C for 24 hours to obtain a solution containing the reaction product. After diluting the mixture to a 20 wt% solution with propylene glycol monomethyl ether, 147.90 g of anion exchange resin (Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 147.90 g of cation exchange resin (Amberlite [registered trademark] 15JWET, Organo Corporation) were added, stirred at 60 °C for 4 hours, filtered, and the resin was separated to obtain compound solution (1-28). The weight average molecular weight Mw measured by GPC in terms of polystyrene was 18,000. [ka]

[0213] [Example 21] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.74 g of compound solution (1-22) (solid content 28.5% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.80 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0214] [Example 22] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.74 g of compound solution (1-21) (solid content 28.7% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.81 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0215] [Example 23] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.89 g of compound solution (1-23) (solid content 26.4% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.66 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0216] [Example 24] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.99 g of compound solution (1-24) (solid content 25.1% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.56 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0217] [Example 25] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.84 g of compound solution (1-25) (solid content 27.2% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.71 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0218] [Example 26] To 3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.84 g of compound solution (1-26) (solid content 26.4% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.66 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0219] [Example 27] To 3.49 g of propylene glycol monomethyl ether acetate (solid content 28.7% by mass) containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.), 0.10 g of propylene glycol monomethyl ether acetate containing 1 mass % surfactant (manufactured by DIC Corporation, Megafac R-40), 1.75 g of compound solution (1-22) (solid content 28.5% by mass), 6.86 g of propylene glycol monomethyl ether acetate, and 2.80 g of propylene glycol monomethyl ether were added and dissolved, and the resulting mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0220] [Example 28] To 3.42 g of propylene glycol monomethyl ether acetate (solid content 28.7% by mass) containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.), 0.10 g of propylene glycol monomethyl ether acetate containing 1 mass % surfactant (manufactured by DIC Corporation, Megafac R-40), 1.72 g of compound solution (1-22) (solid content 28.5% by mass), 1.47 g of propylene glycol monomethyl ether containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 6.92 g of propylene glycol monomethyl ether acetate, and 1.38 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0221] [Example 29] To 4.97 g of compound solution (1-28) (solid content 20.1% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.75 g of compound solution (1-22) (solid content 28.5% by mass), 3.95 g of propylene glycol monomethyl ether acetate, and 4.23 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0222] [Example 30] To 4.87 g of compound solution (1-28) (solid content 20.1% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.72 g of compound solution (1-22) (solid content 28.5% by mass), 1.47 g of propylene glycol monomethyl ether containing 2 mass % of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of propylene glycol monomethyl ether acetate, and 2.89 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0223] [Example 31] To 2.78 g of compound solution (1-21) (solid content: 28.7% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.46 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0224] [Example 32] To 2.80 g of compound solution (1-22) (solid content: 28.5% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.44 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0225] [Example 33] To 3.02 g of compound solution (1-23) (solid content: 26.4% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.21 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0226] [Example 34] To 3.18 g of compound solution (1-24) (solid content: 25.1% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.06 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0227] [Example 35] To 2.94 g of compound solution (1-25) (solid content: 27.2% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.30 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0228] [Example 36] To 3.02 g of compound solution (1-26) (solid content: 26.4% by mass), 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 2.60 g of propylene glycol monomethyl ether acetate, and 4.21 g of propylene glycol monomethyl ether were added and dissolved, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0229] [Example 37] To 2.72 g of the compound solution (1-22) (solid content 28.5% by mass) were added 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.16 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 2.61 g of propylene glycol monomethyl ether acetate, and 3.36 g of propylene glycol monomethyl ether, and the resulting solution was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm, to prepare a solution of a resist underlayer film-forming composition.

[0230] [Comparative Example 21] To 2.62 g of the compound solution (1-27) (solid content 29.9% by mass), 0.08 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.39 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.18 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.74 g of propylene glycol monomethyl ether acetate, and 2.99 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0231] [Comparative Example 22] To 2.62 g of the compound solution (1-27) (solid content 29.9% by mass), 0.08 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.39 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.18 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.74 g of propylene glycol monomethyl ether acetate, and 2.99 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0232] [Comparative Example 23] To 3.42 g of propylene glycol monomethyl ether acetate (solids content 28.7% by mass) containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 0.49 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.47 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 6.92 g of propylene glycol monomethyl ether acetate, and 2.61 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0233] [Comparative Example 24] To 4.87 g of compound solution (1-28) (solid content 20.1% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.49 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.47 g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of propylene glycol monomethyl ether acetate, and 4.12 g of propylene glycol monomethyl ether were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0234] (Test for elution into resist solvent) The resist underlayer film-forming composition solutions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 250°C for 60 seconds or 260°C for 60 seconds to form resist underlayer films (film thickness 0.20 μm). These resist underlayer films were immersed in solvents used in resists: ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. These resist underlayer films were insoluble in these solvents.

[0235] (Confirm the curing end temperature) The resist underlayer film-forming composition solutions prepared in Comparative Examples 21-22 and Examples 21-26 were each applied to a silicon wafer using a spin coater and baked on a hot plate at a given temperature for 60 seconds to form resist underlayer films (film thickness 0.20 μm). The temperature at which these resist underlayer films did not dissolve in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (= cure end temperature) was determined. The method was the same as for the dissolution test in resist solvents (Table 21).

[0236] [Table 21]

[0237] The curing end temperatures of Examples 21 to 26 are higher than those of Comparative Examples 21 and 22. It can be seen that the crosslinking agents used in the examples have higher fluidity and slower curing than when conventional crosslinking agents are used.

[0238] (Optical constant measurement) The solutions of the resist underlayer film-forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied to a silicon wafer using a spin coater. The wafers were baked on a hot plate at 250°C for 60 seconds or 260°C for 60 seconds to form resist underlayer films (film thickness 0.05 μm). The refractive index (n value) and optical absorption coefficient (k value, also called extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer (Table 22).

[0239] [Table 22]

[0240] As can be seen from Examples 31-37, changing the type of epoxy compound can significantly change the optical constants of the crosslinker. Comparing Examples 21-26, which used these crosslinkers, with Comparative Examples 21-22, which used a conventional crosslinker, shows that changing the type of crosslinker can change the optical constants of materials with the same composition ratio. This trend is also seen between Comparative Example 23 and Examples 27-28, and Comparative Example 24 and Examples 30-31, indicating that reflectance can be suppressed by selecting an appropriate crosslinker.

[0241] [Dry etching rate measurement] The etcher and etching gas used to measure the dry etching rate were as follows: there was. RIE-10NR (Samco): CF4 The resist underlayer film-forming composition solutions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied to a silicon wafer using a spin coater. Resist underlayer films (film thickness 0.20 μm) were formed by baking on a hot plate at 250°C for 60 seconds or 260°C for 60 seconds. Dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rate ratios for Comparative Examples 21-24 and Examples 21-37 were calculated. The dry etching rate ratio was the dry etching rate ratio of (resist underlayer film) / (KrF photoresist). (Table 23)

[0242] [Table 23]

[0243] As can be seen from Examples 31-37, the etching rate of the crosslinker can be significantly changed by changing the type of epoxy compound. Comparing Examples 21-26, which used these crosslinkers, with Comparative Examples 21-22, which used a conventional crosslinker, it is possible to change the etching rate of materials with the same composition ratio by changing the type of crosslinker. This trend is also seen between Comparative Example 23 and Examples 27-28, and Comparative Example 24 and Examples 30-31, and adjusting the etching rate appropriately can improve processability.

[0244] (Embeddability evaluation) The embedding ability was confirmed in a dense pattern area of ​​a 200 nm thick SiO2 substrate with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were applied to the substrate and then baked at 250°C for 60 seconds or 260°C for 60 seconds to form resist underlayer films of approximately 200 nm. The planarization of these substrates was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the presence or absence of the resist underlayer film-forming composition filling the interior of the pattern was confirmed (Table 24). When the resist underlayer film was formed without gaps within the pattern, the embedding ability was evaluated as good ("○"), and when it was not embedded within the pattern or holes or gaps were present within the pattern, the embedding ability was evaluated as poor ("×").

[0245] [Table 24]

[0246] Examples 21-37 show embeddability equivalent to that of Comparative Examples 21-24, which used conventional crosslinking agents.

[0247] (Coating test on uneven substrate) In a coating test for a stepped substrate, a comparison was made of the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) on a 200 nm thick SiO2 substrate. The resist underlayer film-forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were applied to the substrate and baked at 250°C for 60 seconds or 260°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the trench area (patterned area) and the open area (non-patterned area) of the stepped substrate (the coating step between the trench area and the open area, referred to as the bias). Here, planarization means that the difference in film thickness (Iso-TRENCH bias) of the coating present on the upper surface of the patterned area (TRENCH (patterned area)) is small between the area where the pattern is present and the area where the pattern is not present (open area (non-patterned area)) (Table 25). Examples in which an improvement of 15 nm or more was confirmed compared to Comparative Example 21 were evaluated as ○, Examples in which an improvement of 30 nm or more was confirmed compared to Comparative Example 21 were evaluated as ⊚, and Comparative Examples in which no improvement was confirmed were evaluated as ×.

[0248] [Table 25]

[0249] Comparing Comparative Example 22 with Examples 21-26, Comparative Example 23 with Examples 27-28, and Comparative Example 24 with Examples 29-30, it was confirmed that the Examples showed significant improvements in planarization properties. Furthermore, Examples 31-37, in which a resist underlayer film was formed using a crosslinking agent or a crosslinking agent and an acid catalyst, also showed significant improvements in planarization properties compared to a general composition such as Comparative Example 22. These results are thought to be due to the fact that the curing end temperature of the crosslinking agent used in the Examples was higher than the curing end temperature when using conventional crosslinking agents, allowing the resin to maintain a longer flow time.

[0250] (Photocuring test) The resist underlayer film-forming compositions prepared in Comparative Examples 21-24 and Examples 22, 26, 31, and 36 were each applied onto a silicon wafer using a spin coater. The composition was heated on a hot plate for 60 seconds at a temperature at which the composition would not completely cure, forming a resist underlayer film. This resist underlayer film was then irradiated with 500 mJ / cm using an ultraviolet irradiation device equipped with a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 The coating film was irradiated with UV light for 1 minute to confirm its solvent removability under light irradiation (UV light irradiation). Solvent removability was evaluated by immersing the UV-irradiated coating film in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate for 1 minute, spin-drying, and then baking at 100°C for 1 minute, and measuring the film thickness (Table 26). Films with a film thickness reduction of 1% or less were marked with an O, and films with a film thickness reduction of 1% or more were marked with an X.

[0251] [Table 26]

[0252] It was confirmed that the inclusion of a crosslinking agent having a non-aromatic unsaturated bond in the molecule provides not only heat curing but also photocuring properties.

[0253] (Coating test on stepped substrate after light irradiation) As a coating test for a stepped substrate, a comparison was made of the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) on which no pattern was formed on a 200 nm thick SiO2 substrate. The resist underlayer film-forming compositions prepared in Examples 22, 26, and 31 were applied to the substrate, and then baked at the temperatures shown in the table to form a resist underlayer film of approximately 200 nm. This resist underlayer film was then baked at 500 mJ / cm using an ultraviolet irradiation device manufactured by Ushio Inc., using a UV irradiation unit (wavelength 172 nm). 2The planarization of the substrates was evaluated using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation in the same manner as in the "Test for coating uneven substrates" (Table 27). The planarization of Examples 22, 26, and 31, which were subjected to heat curing alone, was good (◯). However, it was confirmed that the planarization of these samples was further improved (◎) when they were subjected to heat treatment at a relatively low temperature and then photocuring to complete the curing.

[0254] [Table 27]

[0255] Even with the exact same composition, the planarization properties could be improved by appropriately combining thermal curing and photocuring. [Industrial Applicability]

[0256] According to the present invention, it is possible to provide a resist underlayer film-forming composition that has excellent embedding properties and planarization properties for uneven substrates; a resist underlayer film that is insoluble in a resist solvent, has good optical constants, and a high etching rate, which is formed by applying and baking the composition; and methods for manufacturing a patterned substrate and a semiconductor device that utilize these.

Claims

[Claim 1] A compound represented by the following formulas (1-21) to (1-25). 【Chemistry 163】 (In the formula, each m is independently an integer of 1 to 20, Each r is independently an integer of 0 to 5.

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