Organic resin composition for forming metal oxide resist pattern

Abstract

The present invention relates to an organic film forming composition for use in forming an organic film which is to be formed between resist patterns formed from a metal-containing resist film and is to be removed subsequently. The organic film forming composition contains: an organic polymer having a glass transition temperature of 150°C or higher; and a solvent.

Description

Organic resin composition for forming metal oxide resist patterns

[0001] The present invention relates to a composition for forming an organic film that is used to form an organic film that is formed between resist patterns formed from a metal-containing resist and is then removed.

[0002] Conventionally, microfabrication by lithography using photoresist has been performed in the manufacture of semiconductor devices. This microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developed, and the substrate is then etched using the resulting photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the pattern on the substrate surface.

[0003] As semiconductor devices become more highly integrated, there is a trend toward shorter wavelengths of actinic rays, from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm), and furthermore, exposure techniques using EUV (Extreme Ultra Violet) and electron beams are being considered.

[0004] In order to achieve finer resist patterning, in recent years, lithography techniques using metal oxide resists (MORs, also referred to as metal-containing resists), which have superior etching resistance compared to conventional chemically amplified resists, have been actively developed (see, for example, Patent Document 1, etc.). For further miniaturization in the future, it is essential to reduce the thickness of the resist film, and this metal oxide resist (MOR) (hereinafter also referred to as "metal-containing resist") has sufficient etching resistance to perform fine patterning even in a thin film, and therefore has been expected in recent years to be a material used in next-generation EUV lithography techniques.

[0005] JP 2011-253185 A

[0006] As resist patterns formed from metal-containing resists become finer, resist pattern collapse becomes a problem. Furthermore, as resist patterns become finer, variations in resist pattern dimensions (e.g., LWR (line width roughness)) become a problem.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic film-forming composition that can suppress variations in resist pattern dimensions while preventing resist pattern collapse in fine patterning using a metal-containing resist film, and a method for manufacturing a semiconductor element using the organic film-forming composition.

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0009] That is, the present invention encompasses the following: [1] A composition for forming an organic film used to form an organic film that is formed between resist patterns formed from a metal-containing resist film and is subsequently removed, the composition comprising an organic polymer having a glass transition temperature of 150°C or higher and a solvent. [2] The composition for forming an organic film according to [1], wherein the metal-containing resist film contains at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co. [3] The composition for forming an organic film according to [1] or [2], wherein the organic polymer has a glass transition temperature of 150°C to 350°C. [4] The composition for forming an organic film according to any one of [1] to [3], wherein the organic polymer is a resin (G) having a composite unit structure, the composite unit structure comprising: a unit structure (A) having an aromatic ring; and a unit structure (B) having one or more carbon atoms, and wherein the resin is obtained by a reaction that forms a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B). [5] The composition for forming an organic film according to [4], wherein the unit structure (A) has at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. [6] The composition for forming an organic film according to [4] or [5], wherein the unit structure (B) is a unit structure derived from an aldehyde compound or an aldehyde equivalent, and the aldehyde equivalent is an organic compound capable of forming a covalent bond with an aromatic ring, and is an organic compound having a ketone group, an acetal group, a ketal group, a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a hydroxyl group, an alkoxy group or a halo group bonded to the α-carbon atom of an alkylaryl group, or a carbon-carbon unsaturated bond. [7] The composition for forming an organic film according to any one of [1] to [6], wherein the organic polymer has a composite unit structure represented by any one of the following formulas (G-1), (G-2), (G-3-1), and (G-3-2): (In formulas (G-1), (G-2), (G-3-1) and (G-3-2), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２ R each independently represents an aromatic ring. １０１ , R １０２ , R １１１ , R １１２ , R １２１ , R １２２ , R １２４ , R １３１ , and R １３２ R each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 80 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, a sulfide bond, a sulfonyl group, a carboxyl group, or an ester bond. １０３ , R １１３ , R １２３ , and R １３３ are each independently 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 alkynyl 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. １０１ , n １０２ , n １１１ , n １１２ , n １２１ , n １２２, n １３１ , and n １３２ Each of n independently represents 0 or an integer up to the maximum number that can be substituted on an aromatic ring. １２４ represents 0 or 1.) [8] Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２each independently represent a benzene ring or a naphthalene ring. [9] The composition for forming an organic film according to [7] or [8], wherein in formula (G-1), formula (G-2), formula (G-3-1), and formula (G-3-2), at least one of R and R' each independently represents an aromatic ring having 6 to 30 carbon atoms which may have a substituent, or R and R' together with the carbon atom bonded thereto represent a structure having a ring structure, and the ring structure has an aromatic ring.

[10] The composition for forming an organic film according to any of [1] to [9], which is used to prevent the resist pattern from collapsing.

[11] The composition for forming an organic film according to any of [1] to

[10] , which also serves as a developer when forming the resist pattern.

[12] A method for manufacturing a semiconductor device, comprising: a step of irradiating a metal-containing resist film with light or an electron beam; a step of contacting the metal-containing resist film irradiated with light or an electron beam with a developer to obtain a resist pattern; a step of applying the organic film-forming composition according to any one of [1] to

[10] onto the resist pattern without drying the resist pattern in contact with the developer to form an organic film between the resist patterns; and a step of removing the organic film.

[13] A method for manufacturing a semiconductor device according to

[12] , wherein the organic film is also formed on the resist pattern in the step of forming the organic film.

[14] A method for manufacturing a semiconductor device according to

[12] or

[13] , wherein the step of removing the organic film is selected from dry etching, wet etching, radiation etching, high-temperature baking, dissolution removal using a solvent, and ozone treatment.

[15] A substrate with a metal-containing resist pattern, formed by applying the organic film-forming composition according to any one of [1] to

[10] onto a metal-containing resist pattern, so that an organic film is embedded between the metal-containing resist patterns.

[0010] According to the present invention, it is possible to provide an organic film-forming composition that can prevent resist pattern collapse and suppress variation in resist pattern dimensions in fine patterning using a metal-containing resist film, and a method for manufacturing a semiconductor element using the organic film-forming composition.

[0011] FIG. 1A is a cross-sectional view (part 1) illustrating one embodiment of a method for manufacturing a semiconductor element. FIG. 1B is a cross-sectional view (part 2) illustrating one embodiment of a method for manufacturing a semiconductor element. FIG. 1C is a cross-sectional view (part 3) illustrating one embodiment of a method for manufacturing a semiconductor element. FIG. 1D is a cross-sectional view (part 4) illustrating one embodiment of a method for manufacturing a semiconductor element. FIG. 1E is a cross-sectional view (part 5) illustrating one embodiment of a method for manufacturing a semiconductor element. FIG. 2 is a cross-sectional view (part 1) illustrating one aspect of an organic film between resist patterns. FIG. 3A is a cross-sectional view (part 1) illustrating another embodiment of a method for manufacturing a semiconductor element. FIG. 3B is a cross-sectional view (part 2) illustrating another embodiment of a method for manufacturing a semiconductor element. FIG. 3C is a cross-sectional view (part 3) illustrating another embodiment of a method for manufacturing a semiconductor element. FIG. 3D is a cross-sectional view (part 4) illustrating another embodiment of a method for manufacturing a semiconductor element.

[0012] (Organic Film-Forming Composition) The organic film-forming composition of the present invention is a composition used for forming an organic film that is formed between resist patterns formed from a metal-containing resist film and is subsequently removed. The organic film-forming composition contains an organic polymer having a glass transition temperature of 150° C. or higher and a solvent.

[0013] The present inventors have found that when forming a resist pattern from a metal-containing resist film, resist pattern collapse is likely to occur after development. Generally, in forming a resist pattern, drying is performed to remove the developer after development. After extensive research, the present inventors have found that resist pattern collapse can be prevented by forming an organic film between the resist patterns after development and then removing the organic film, rather than drying and removing the developer after development. The present inventors believe that resist pattern collapse occurs due to the influence of capillary forces of the developer during drying to remove the developer. Furthermore, the present inventors have focused on improving the dimensional variation of the resist pattern. They have found that the dimensional variation of the resist pattern can be suppressed by increasing the glass transition temperature (e.g., 150°C or higher) of the organic polymer constituting the organic film formed between the resist patterns, leading to the completion of the present invention.

[0014] Incidentally, WO 2012 / 128251 discloses a developer used in a lithography process, which contains a polymer for forming a dry etching mask and an organic solvent (see, for example, claim 1). However, the technical concept of this developer is clearly different from that of the present invention in that the developer is used to form a reverse pattern using the polymer contained therein.

[0015] Furthermore, Japanese Patent Laid-Open Publication No. 2011-33842 discloses a processing solution for pattern formation using a chemically amplified resist composition, the processing solution containing an organic solvent-soluble resin and an organic solvent (see, for example, claim 1). According to paragraph

[0013] of Japanese Patent Laid-Open Publication No. 2011-33842, this technology presumably contributes to improving the dissolution rate by promoting the penetration of a developer or rinse solution into the resist composition. In contrast, the present invention uses a metal-containing resist film as the resist film. Since resins and metal-containing resist films are typically incompatible, when the resist film is a metal-containing resist film, it is not expected that an organic solvent-soluble resin will promote the penetration of a developer or rinse solution into the resist composition. In this respect, the technical concept of the invention described in Japanese Patent Laid-Open Publication No. 2011-33842 and the present invention are clearly different.

[0016] The metal-containing resist film is not particularly limited, but preferably contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0017] The organic film-forming composition is preferably used to prevent the resist pattern from collapsing, and is preferably used to suppress variations in the dimensions of the resist pattern.

[0018] The organic film-forming composition also serves as a developer when forming a resist pattern, for example.

[0019] The method for removing the organic film is not particularly limited, and examples thereof include methods for removing organic films used in semiconductor lithography processes. Examples of methods for removing the organic film include dry etching, wet etching (e.g., decomposition and removal using an acidic solution), radiation etching, high-temperature baking, dissolution and removal using a solvent, and ozone treatment. These methods can be used alone or in combination of two or more.

[0020] <Organic Polymer> The organic polymer has a glass transition temperature of 150°C or higher. By forming an organic film between resist patterns using the organic film-forming composition, it is possible to prevent the resist pattern from collapsing. Furthermore, since the organic film-forming composition contains an organic polymer with a relatively high glass transition temperature, the organic film formed between the resist patterns can suppress variation in the dimensions of the resist pattern.

[0021] The glass transition temperature of the organic polymer is not particularly limited as long as it is 150°C or higher. There is no particular upper limit to the glass transition temperature of the organic polymer, and the glass transition temperature of the organic polymer may be 400°C or lower, 350°C or lower, or 300°C or lower. The glass transition temperature of the organic polymer is determined, for example, using a differential scanning calorimeter. Specifically, for example, the glass transition temperature of the organic polymer can be determined under the following conditions. Differential scanning calorimeter: DSC Q2000 (manufactured by TA Instruments) Temperature range: room temperature to 350°C Heating rate: 5°C / min Heating rate: 5°C / min Atmosphere: nitrogen The endothermic onset temperature during the second heating is taken as the glass transition temperature. The endothermic onset temperature is the point of intersection between the baseline up to the start of endothermic absorption and the tangent to the endothermic curve. When the glass transition temperature of the organic polymer is significantly higher than 300°C, the upper limit of the measurement temperature range can be changed to 400°C or 450°C for measurement.

[0022] The organic polymer is not particularly limited as long as it has a glass transition temperature of 150°C or higher, and examples thereof include polyester resins, polyamide resins, polyimide resins, polyether ketone resins, and resin (G) described below, with resin (G) described below being preferred.

[0023] <<Resin (G)>> An example of an organic polymer is a resin (G) having a complex unit structure. The complex unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. The resin (G) is a resin obtained by a reaction that forms a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B). In this specification, the resin (G) may be referred to as a "novolac resin."

[0024] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting an aromatic ring or an atom bonded to an aromatic ring.

[0025] The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The aldehyde equivalent is an organic compound capable of forming a covalent bond with an aromatic ring, and is an organic compound having a ketone group, an acetal group, a ketal group, a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a hydroxyl group, an alkoxy group or a halo group bonded to the α-carbon atom of an alkylaryl group, or a carbon-carbon unsaturated bond.

[0026] [I. Definitions of Terms] In this specification, definitions of main terms related to the novolac resin, which is one embodiment of the present invention, are explained below. Unless otherwise specified, the following definitions of each term apply to the novolac resin.

[0027] (I-1) "Novolac Resin" The term "novolac resin" is used in a broad sense to encompass not only phenol-formaldehyde resins (so-called novolac phenolic resins) and aniline-formaldehyde resins (so-called novolac aniline resins) in the narrow sense, but also resins formed by forming a covalent bond (substitution reaction, addition reaction, condensation reaction, addition-condensation reaction, etc.) between an organic compound having a functional group capable of forming a covalent bond with an aromatic ring (for example, an aldehyde group; a ketone group; an acetal group; a ketal group; a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group; or a carbon-carbon unsaturated bond such as in divinylbenzene or dicyclopentadiene) in the presence of an acid catalyst or under equivalent reaction conditions, and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen, nitrogen, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring)

[0028] Therefore, the novolak resin referred to in this specification is a resin formed by linking a plurality of compounds having aromatic rings together, with an organic compound containing a carbon atom derived from the functional group (sometimes referred to as a "linking carbon atom") forming a covalent bond with an aromatic ring in a compound having an aromatic ring via the linking carbon atom.

[0029] In this specification, the terms unit structure (A) and unit structure (B) are used to refer to unit structures constituting a "novolac resin." Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure (A).

[0030] (I-2) "Residue" A "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or a heteroatom (such as a nitrogen atom, oxygen atom, or sulfur atom) is replaced with a bond, and may be a monovalent group or a polyvalent group. For example, replacing one hydrogen atom with one bond results in a monovalent organic group, and replacing two hydrogen atoms with bonds results in a divalent organic group.

[0031] (I-3) "Aromatic Ring" (Aromatic Group, Aryl Group, Arylene Group) The term "aromatic ring" refers to a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof [sometimes referred to as "aromatic groups," "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)], and encompasses not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocycle is an aromatic monocycle, and the remaining monocycles that form a fused ring with the aromatic monocycle may be a monocyclic heterocycle (heteromonocycle) or a monocyclic alicyclic hydrocarbon (alicyclic monocycle). In this specification, heteroaryl groups are included in the aryl group. Heteroarylene groups are included in the arylene group.

[0032] Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzanthracene, pyrene, chrysene, fluorene, biphenyl, corannulene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, and cyclooctatetraene, more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; and aromatic hydrocarbon rings such as furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, and pyrrolidone. aromatic heterocycles such as indole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole, and more typically, furan, thiophene, pyrrole, indole, phenylindole, bisindolefluorene, phenothiazine, carbazole, and indolocarbazole, but are not limited thereto.

[0033] The aromatic ring (for example, a benzene ring, a naphthalene ring, etc.) may have an optional substituent, and examples of such a substituent include the following atoms and groups: a halogen atom; a saturated or unsaturated, linear, branched, or cyclic hydrocarbon group (-R ａ ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), and aryl groups, whose hydrocarbon chains may be interrupted one or more times by oxygen atoms), -OR (wherein R is the hydrocarbon group -R ａ ) Aryloxy group -NH ２ , —NHR or —NR ２ (Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ - Hydroxyl group - Hydroxyalkyl group - Carboxyl group - Formyl group - Cyano group - Nitro group - Ester group (for example, -CO ２ R or -OCOR, where R is the hydrocarbon group -R ａ an amide group [for example, —NHCOR, —CONHR, —NRCOR (wherein the two Rs may be the same or different), or —CONR ２ (Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ a sulfonyl-containing group (e.g., —SO ２ R, where R is the hydrocarbon group -R ａ or a hydroxyl group -OH.) a thiol group (-SH) a sulfide-containing group (-SR, where R is the hydrocarbon group -R ａ represents an organic group containing an ether bond [R １１ -O-R １１ (R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group or a pyrenyl group; a residue of an ether compound represented by the formula (I); an organic group containing an ether bond, such as a methoxy group, an ethoxy group or a phenoxy group]

[0034] The term "aromatic ring" also includes organic groups having one or more fused rings of aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) with one or more fused aliphatic or heterocyclic rings. Examples of the aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene. Examples of the heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0035] The "aromatic ring" may be an organic group having a structure in which two or more aromatic rings are linked by a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ The divalent linking group may also be a divalent group in which one hydrogen atom has been removed from any of the substituents of the aromatic rings described above.

[0036] (I-4) "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and is a concept that encompasses not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic, at least one monocyclic ring is a heteromonocyclic ring, but the remaining monocyclic rings may be aromatic hydrocarbon monocyclic or alicyclic monocyclic. For the aromatic heterocycle, the examples in (I-3) above can be referred to. As with the aromatic ring in (I-3) above, it may have a substituent.

[0037] (I-5) "Non-aromatic ring" (aliphatic ring) When the "non-aromatic ring" is a monocycle, the "non-aromatic monocycle" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocycle of an alicyclic compound. It may also be called an aliphatic monocycle (which may include an aliphatic heteromonocycle, or may contain an unsaturated bond as long as it does not belong to the aromatic compound). As with the aromatic ring of (I-3) above, it may have a substituent.

[0038] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0039] When the "non-aromatic ring" is a polycyclic ring, the "non-aromatic polycyclic ring" refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic ring of an alicyclic compound. It may also be called an aliphatic polycyclic ring (which may include an aliphatic heteropolycyclic ring (at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring), or may contain an unsaturated bond as long as it does not belong to the aromatic compound). It includes a non-aromatic bicyclic ring, a non-aromatic tricyclic ring, and a non-aromatic tetracyclic ring.

[0040] When the "non-aromatic ring" is a bicycle, the "non-aromatic bicycle" refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of two alicyclic compounds. In this specification, it may also be referred to as an aliphatic bicycle (which may include an aliphatic heterobicycle, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Examples of non-aromatic bicycles include bicyclopentane, bicyclooctane, and bicycloheptene.

[0041] When the "non-aromatic ring" is a tricycle, the "non-aromatic tricycle" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of three alicyclic compounds (each of which may be a heterocycle or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tricycles include tricyclooctane, tricyclononane, and tricyclodecane.

[0042] When the "non-aromatic ring" is a tetracyclic ring, the "non-aromatic tetracyclic ring" refers to a fused ring composed of four monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of four alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tetracyclic rings include hexadecahydropyrene.

[0043] (I-6) The term "carbon atoms constituting a ring (moiety)" refers to the carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring) in an unsubstituted state.

[0044] (I-7) The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0045] (I-8) In the chemical structural formula showing the unit structure of the novolak resin in this specification, a bond (indicated by *) may be shown for convenience. However, unless otherwise specified, such a bond can be at any available bonding position in the unit structure, and does not in any way limit the bonding position in the unit structure.

[0046] Resin (G) has a complex unit structure, which includes a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0047] The composite unit structure of the resin (G) is represented, for example, by the following formula (AB). (In formula (AB), A represents the unit structure (A), and B represents the unit structure (B).)

[0048] <<A-1: Unit Structure (A)>> The unit structure (A) has an aromatic ring. The unit structure (A) has, for example, at least one of an oxygen atom constituting the aromatic ring, a sulfur atom constituting the aromatic ring, an oxygen atom bonded to the aromatic ring, a nitrogen atom constituting the aromatic ring, and a nitrogen atom directly bonded to the aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting the aromatic ring or an atom bonded to the aromatic ring.

[0049] The number of carbon atoms contained in the unit structure (A) is not particularly limited, but is, for example, 4 to 100, and preferably 4 to 50.

[0050] Preferably, such aromatic rings have from 4 to 30, or from 6 to 30, more preferably from 4 to 24, or from 6 to 24 carbon atoms.

[0051] Preferably, such aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, or pyrene rings; or a condensed ring of a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring with a heterocycle or an aliphatic ring (such as a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, an indole ring, a carbazole ring, or an indolocarbazole ring).

[0052] The aromatic ring may have any substituent, and from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary number of heteroatoms.In addition, the aromatic ring may have two or more aromatic rings connected by a linking group, and the linking group may contain the minimum necessary number of heteroatoms.Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0053] The "aromatic ring" may contain at least one heteroatom selected from N, S and O on, within or between the rings.

[0054] Examples of heteroatoms that may be contained on the ring include nitrogen atoms contained in amino groups (e.g., propargylamino groups) and cyano groups; oxygen atoms contained in oxygen-containing substituents such as formyl groups, hydroxy groups, carboxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups (e.g., propargyloxy groups), and aryloxy groups; and nitrogen atoms and oxygen atoms contained in nitro groups, which are oxygen-containing and nitrogen-containing substituents. Examples of heteroatoms that may be contained in the ring include oxygen atoms contained in furan and xanthene, nitrogen atoms contained in carbazole and pyrrole, and sulfur atoms contained in phenothiazine. Examples of heteroatoms that may be contained in the linking group of two or more aromatic rings include -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２Examples of the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. In this specification, "an atom constituting an aromatic ring" is synonymous with "an atom contained within the ring." "An atom bonded to an aromatic ring" refers to, for example, "an atom directly bonded to the ring among atoms or groups contained on the ring" and "an atom directly bonded to the ring among atoms contained between rings." For example, the atoms constituting a benzene ring are carbon atoms. For example, the atoms constituting a pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of a hydroxyl group in phenol is not an atom constituting an aromatic ring. For example, the oxygen atom of a hydroxyl group in phenol is an atom bonded to the benzene ring, and is an atom directly bonded to the benzene ring among groups contained on the benzene ring.

[0055] <<A-2: Examples of Skeletons Constituting the Unit Structure (A)>> The unit structure (A) has, for example, a skeleton having an aromatic ring.

[0056] The skeleton having an aromatic ring is preferably an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, or a phenol skeleton.

[0057] The unit structure (A) is, for example, a residue obtained by removing two hydrogen atoms from a skeleton having an aromatic ring. The skeleton having an aromatic ring is derived, for example, from a compound having an aromatic ring when synthesizing the resin (G). The skeleton having an aromatic ring is, for example, a residue obtained by removing two hydrogen atoms from a compound having an aromatic ring when synthesizing the resin (G).

[0058] The skeleton having an aromatic ring may have a substituent. Examples of the substituent include a halo group (halogen atom), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxyl group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, and an ether bond-containing group. Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Examples of the alkenyl group include linear, branched, or cyclic alkenyl groups having 2 to 10 carbon atoms. Examples of the alkynyl group include linear, branched, or cyclic alkynyl groups having 2 to 10 carbon atoms. Examples of the alkoxy group include a group represented by -OR. Here, R represents a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R ａ The alkoxy group may have, for example, 1 to 20 carbon atoms. The aryloxy group may have 6 to 30 carbon atoms. The amino group may be -NH ２ , —NHR or —NR ２ Here, R is the hydrocarbon group -R ａ represents -NR ２ In the formula, the two R's may be the same or different. Examples of the hydroxyalkyl group include linear, branched, and cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of the ester group include -CO ２ Examples of the hydrocarbon group include a group represented by -R or -OCOR. ａ The amide group is —NHCOR, —CONHR, —NRCOR, or —CONR ２ Here, R is the hydrocarbon group -R ａ When there are two R's, the two R's may be the same or different. The sulfonyl-containing group includes -SO ２ Here, R is the hydrocarbon group -Rａ or a hydroxy group -OH. Examples of sulfide-containing groups include groups represented by -SR, where R is the hydrocarbon group -R ａ The ether bond-containing group is represented by R １１ -O-R １１ In this case, R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group.

[0059] <<<A-2-1: Aromatic Amine Skeleton>>> The aromatic amine skeleton refers to a skeleton having an aromatic ring and a nitrogen atom that is bonded to the aromatic ring but does not constitute a ring. Examples of the aromatic amine skeleton include skeletons represented by the following formulas (A-1a) to (A-1c). As described below, in the unit structure (A), the hydrogen atom of the NH group may be replaced with a substituent. Examples of the substituent include the substituents described in the above (I-3) "Aromatic Ring" and the substituents (S) represented by the below-described formulas (S1) to (S7). (In formulas (A-1a) to (A-1c), Ar １１ R each independently represents a residue of an aromatic ring. １１ each independently represents a hydrogen atom or a residue of an aromatic ring.

[0060] Ar １１ and R １１ Examples of the aromatic ring in the residue of the aromatic ring include aromatic rings represented by the following formula (G1): These aromatic rings may have a substituent.

[0061] Examples of the skeleton represented by formula (A-1a) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atom of the NH group may be replaced with a substituent. The same applies to the following skeletons.

[0062] Examples of the skeleton represented by formula (A-1b) include the following skeletons:

[0063] Examples of the skeleton represented by formula (A-1c) include the following skeletons:

[0064] <<<A-2-2: Nitrogen-Containing Aromatic Heterocyclic Skeleton>>> The nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton having an aromatic heterocycle having a nitrogen atom among the atoms constituting the heterocycle. Examples of the nitrogen-containing aromatic heterocycle include a pyrrole ring, an indole ring, a carbazole ring, a pyridine ring, an acridine ring, a phenoxazine ring, and a phenothiazine ring. These nitrogen-containing aromatic heterocycles may have a substituent. Examples of the nitrogen-containing aromatic heterocyclic skeleton include skeletons represented by the following formula (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), (A-2c-4), (A-2d), (A-2e), (A-3a), or (A-3b). As will be described later, in the structural unit (A), the hydrogen atom of the NH group may be replaced with a substituent. (In the formula, Ar ２１ R each independently represents a residue of an aromatic ring. ２１ R each independently represents a hydrogen atom or a residue of an aromatic ring. ２２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a residue of an aromatic ring. ２２may be joined together to form an unsaturated aliphatic ring. One of the unsaturated bonds in the unsaturated aliphatic ring refers to an unsaturated bond constituting a pyrrole ring. Each R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond to L. L represents a single bond or a linking group. n1 represents 1, and n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, the partial structure (In1) and the partial structure (In2), and the partial structure (Ca1) and the partial structure (Ca2), respectively, are bonded by two nitrogen atoms bonding together, or by two Ar ２１ or a nitrogen atom and Ar ２１ In formula (A-2b-2) and formula (A-2c-4), when L is a linking group, L is N or Ar ２１ is bonded to

[0065] Ar ２１ , R ２１ , R ２２ and the aromatic ring in the residue of the aromatic ring of R includes, for example, an aromatic ring represented by the following formula (G2): These aromatic rings may have a substituent.

[0066] Two adjacent R ２２ Examples of the unsaturated aliphatic ring formed by combining these include the following rings: These aliphatic rings may have a substituent.

[0067] Examples of the linking group for L include a saturated hydrocarbon group having 1 to 5 carbon atoms and a valence of (n1+n2), and a residue obtained by removing (n1+n2) hydrogen atoms from an aromatic ring.

[0068] <Formula (A-2d)> (In formula (A-2d), R １１ each independently represents a hydrogen atom or an aromatic group, Ar is an aromatic ring moiety, each independently representing a benzene ring, a fused ring composed of 2 to 3 benzene rings, or a structure represented by the following formula (Ar01), ０ represents a single bond, —O—, —S—, or —NR１２ -or-CR １３ R １４ represents -, and R １２ is R １１ Same or different from R １１ is the same as the definition of R １３ and R １４ each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n is 1 or 2, when n is 1, Z represents a monovalent organic group, and when n is 2, Z represents a divalent organic group.

[0069] In the unit structure (A), R in formula (A-2d) １１ may be a substituent. １１ is a substituent or an aromatic group, R １１ represents, for example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) may be further substituted with an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, or an arylene group.

[0070] An example of the skeleton represented by formula (A-2d) is the skeleton represented by the following formula (A-2d-1). (R in formula (A-2d-1) １１ , Ar, and X ０ respectively represent R in formula (A-2d). １１ , Ar, and X ０ It is synonymous with R ２１ is an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.

[0071] Ar in formula (A-2d) and formula (A-2d-1) is, for example, a benzene ring or a naphthalene ring. Ar in formula (A-2d) and formula (A-2d-1) may have a structure represented by the following formula (Ar01): (R in formula (Ar01) １１ａ represents R in formula (A-2d-1). １１ is synonymous with R ２１ａ represents R in formula (A-2d-1). ２１ and Ar ａ has the same meaning as Ar in formula (A-2d-1), and X ０ａ represents X in formula (A-2d-1). ０ In the case where two carbon atoms a and b, b and c, or c and d in formula (Ar01) are bonded to each other, X in formula (A-2d) or formula (A-2d-1) ０ forms a condensed ring with the monocyclic moiety containing

[0072] Here, X ０ The monocyclic moiety containing the following formula (AP011) in formula (A-2d) represents a monocyclic ring represented by the following formula (AP011):

[0073] As the skeleton represented by formula (A-2d), a skeleton represented by formula (A-2d-1) above, a skeleton represented by formula (A-2d-2) below, or a skeleton represented by formula (A-2d-3) below is preferred. (In formula (A-2d-2) and formula (A-2d-3), R １１ , Ar, and X ０ respectively represent R in formula (A-2d). １１ , Ar, and X ０ L represents a single bond or a divalent linking group, and examples of the divalent linking group include -O-, -S-, and -SO ２ -, -CO-, -CONH-, -COO-, -NR １０１ -, - (CR １０２ R １０３ ) m １ -, -(Ar １０１ ) m ２ -, -CH ２ -(Ar １０１ ) m ２ -CH ２ - or -(cyclo-R)-. １０１, R １０２ , and R １０３ each independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10. １０１ each independently represents an arylene group having 6 to 30 carbon atoms; m ２ represents an integer of 1 to 3, which is the number of aromatic rings bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring, preferably a 6- to 8-membered ring, which may form a condensed ring with one or two benzene or naphthalene rings. R ２２ each independently represents an optionally substituted arylene group having 6 to 30 carbon atoms, an optionally substituted alkenylene group having 2 to 10 carbon atoms, or an optionally substituted alkynylene group having 2 to 10 carbon atoms.

[0074] <Formula (A-2e)> (In formula (A-2e), L represents a single bond or a divalent linking group between any two carbon atoms constituting each azaaryl fused ring, R １１ and R ２１ each independently represents a hydrogen atom or a residue of an aromatic ring; １２ and R ２２ each independently represents a substituent, n1 and n2 each independently represent R １２ and R ２２ represents the number of substituents, which may be 0, １ and Ar ２ are each independently a benzene ring or a fused ring composed of 2 to 3 benzene rings, which forms a fused ring with the pyrrole ring moiety in formula (A-2e).

[0075] In the unit structure (A), R in formula (A-2e) １１ and R ２１ may be a substituent. １１ and R ２１ is a substituent or a residue of an aromatic group, R １１ and R ２１represents, for example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) may be further substituted with an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, or an arylene group.

[0076] In formula (A-2e), L is a single bond or a divalent linking group. L may be bonded to any carbon atom constituting each azaaryl fused ring, and Ar １ and Ar ２ , i.e., in the azaaryl fused ring and However, it is preferably bonded to a carbon atom constituting the pyrrole ring moiety in the azaaryl fused ring.

[0077] Preferred linking groups (L) include —O—, —S—, and —SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR １０２ R １０３ ) m １ -, - (Ar １０１ ) m ２ -, -CH ２ -(Ar １０１ ) m ２ -CH ２ -, and -(cyclo-R)-. １０２ and R １０３ each independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10. １０１ each represents an arylene group having 6 to 30 carbon atoms; m ２represents the number of aromatic rings bonded to each other by single bonds, an integer of 1 to 3. "cyclo-R" represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring, preferably a 6- to 8-membered ring, which may form a condensed ring with one or two benzene rings or naphthalene rings.

[0078] <Formula (A-3a) and Formula (A-3b)> (In the formula, Ar ３１ and Ar ３２ each independently represents a residue of an aromatic ring, or together with the carbon atom bound thereto represents a residue of an aromatic ring. X is —O, —S—, —NH—, —CH ２ -, -CH ２ -CH ２ - or -CH=CH-.)

[0079] Ar ３１ and Ar ３２ Examples of the aromatic ring in the residue of the aromatic ring of Ar include the aromatic ring represented by the above formula (G1). ３１ and Ar ３２ Examples of the aromatic ring that is formed by combining with the carbon atom to which it is bonded include a fluorene ring, a benzofluorene ring, and a dibenzofluorene ring.

[0080] Examples of the skeleton represented by formula (A-2a) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atoms of the NH groups may be replaced with substituents. The same applies to the following skeletons.

[0081] Examples of the skeleton represented by formula (A-2b-1) include the following skeletons:

[0082] Examples of the skeleton represented by formula (A-2b-2) include the following skeletons:

[0083] Examples of the skeleton represented by formula (A-2c-1) include the following skeletons:

[0084] Examples of the skeleton represented by formula (A-2c-2) or formula (A-2c-3) include the following skeletons.

[0085] Examples of the skeleton represented by formula (A-2c-4) include the following skeletons:

[0086] Examples of the skeleton represented by formula (A-2d) include the following skeletons:

[0087] Examples of the skeleton represented by formula (A-2e) include the following skeletons: Note that specific examples of the skeleton represented by formula (A-2d) and specific examples of the skeleton represented by formula (A-2e) may overlap.

[0088] Examples of the skeleton represented by formula (A-3a) include the following skeletons:

[0089] Examples of the skeleton represented by formula (A-3b) include the following skeletons:

[0090] Other examples of the nitrogen-containing aromatic heterocyclic skeleton include the following skeletons.

[0091] <<<A-2-3: Phenol Skeleton>>> The phenol skeleton refers to a skeleton having an aromatic ring and a hydroxy group bonded to the aromatic ring. The number of hydroxy groups bonded to the aromatic ring of the phenol skeleton is not particularly limited and may be one or more. When there are more than one hydroxy groups, the number may be 2 to 10 or 2 to 8. When there are more than one hydroxy groups, the hydroxy groups may be bonded to the same aromatic ring (for example, a benzene ring) or to different aromatic rings. As described below, in the unit structure (A), the hydrogen atom of the hydroxy group bonded to the aromatic ring may be replaced with a substituent. Examples of the substituent include the substituents described in (I-3) "Aromatic Ring" above, and the substituents (S) represented by Formulas (S1) to (S7) described below.

[0092] Examples of the phenol skeleton include skeletons represented by the following formula (A-4). The aromatic ring in these skeletons may have a substituent, and the hydrogen atom of the hydroxy group may be substituted with a substituent. The same applies to the following skeletons. (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent an integer of 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent an integer of 0 to 4, provided that the sum of n3a and n3b ​​is 1 or more, the sum of n7a and n7b is 1 or more, and the sum of n8a and n8b is 1 or more.)

[0093] Examples of the phenol skeleton include skeletons represented by the following formula (A-5a), (A-5b), (A-5c), or (A-5d). (In the formula, Ar ４１ each independently represents a residue of an aromatic ring; k1 and k2 each independently represent an integer of 1 or 2. X １ is -O-, -CO-, -S-, -SO ２ - or an alkylene group optionally substituted with a halogen atom. ２１ represents a single bond, —O—, —CO—, —S—, or —SO ２When k2 is 1, X represents - or an alkylene group which may be substituted with a halogen atom. ２２ represents a single bond, —O—, —CO—, —S—, or —SO ２ When k1 is 2, X represents - or an alkylene group which may be substituted with a halogen atom. ２１ represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom; ２２ represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. １ represents a trivalent saturated hydrocarbon group. ２ represents a tetravalent saturated hydrocarbon group. m1 and m2 each independently represent an integer of 0 to 3, provided that the sum of m1 and m2 is 1 or more. m3 to m5 each independently represent an integer of 0 to 3, provided that the sum of m3 to m5 is 1 or more. m6 to m8 each independently represent an integer of 0 to 3, provided that the sum of m6 to m8 is 1 or more. m9 to m12 each independently represent an integer of 0 to 3, provided that the sum of m9 to m12 is 1 or more.

[0094] Ar ４１ Examples of the aromatic ring in the residue of the aromatic ring include aromatic rings represented by the following formula (G3): These aromatic rings may have a substituent.

[0095] X １ , and X ２ The number of carbon atoms in the alkylene group which may be substituted with a halogen atom in the formula (I) is, for example, 1 to 20. The structure of the alkylene group may be, for example, linear, branched, cyclic, or a combination of two or more thereof. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0096] Y １ , and Y ２ The number of carbon atoms in the saturated hydrocarbon group in the formula (I) is, for example, 1 to 20. The structure of the saturated hydrocarbon group may be, for example, linear, branched, or cyclic, or a combination of two or more thereof.

[0097] Examples of the phenol skeleton include skeletons represented by the following formula (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d). (In formula (A-6a), formula (A-6b-1), formula (A-6b-2), formula (A-6c), and formula (A-6d), Ar ５１ each independently represents a residue of an aromatic ring. Each n11 independently represents an integer of 1 to 4. Each p independently represents 0 or 1. When p is 1, the oxygen atom forms an ether bond to bridge the aromatic rings, and when p is 0, there is no ether bond to form a bridge between the aromatic rings. L represents a single bond or a divalent linking group.

[0098] Ar ５１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the above formula (G1), and a benzene ring or a naphthalene ring is preferred. Examples of L include divalent groups obtained by removing two hydrogen atoms from the following structure:

[0099] For example, n11 each independently represents 1 or 2.

[0100] Examples of the phenol skeleton include skeletons represented by the following formula (A-7a), (A-7b), or (A-7c). (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar ６１ each independently represents a residue of an aromatic ring; and each n21 independently represents an integer of 1 to 4.

[0101] Ar ６１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the above formula (G1), and a benzene ring and a naphthalene ring are preferred. n21 each independently represents 1 or 2, for example.

[0102] Furthermore, examples of the phenol skeleton include skeletons represented by the following formula (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2). In formula (A-8a-1), formula (A-8b), formula (A-8c), formula (A-8e), formula (A-8f), formula (A-8g-1), and formula (A-8g-2), n31 each independently represents an integer of 1 to 4. In formula (A-8a-2), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8d), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8b), X １ represents —O— or —NH—. ２ is —O—, —S—, or —CH ２ In formula (A-8e), X ３ is -S-, -CH ２ In formula (A-8f), X represents - or -NH-. ４ represents —CO— or —O—, and X ５ is -CH ２ represents - or -O-.)

[0103] For example, n31 each independently represents 1 or 2. n32 and n33 each independently represents 0, 1 or 2.

[0104] Examples of the skeleton represented by formula (A-4) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atoms of the hydroxy groups may be substituted with a substituent. The same applies to the following skeletons.

[0105] Examples of the skeleton represented by formula (A-5a) include the following skeletons:

[0106] Examples of the skeleton represented by formula (A-5b) include the following skeletons:

[0107] Examples of the skeleton represented by formula (A-5c) include the following skeletons:

[0108] Examples of the skeleton represented by formula (A-5d) include the following skeletons:

[0109] Examples of the skeleton represented by formula (A-6a) include the following skeletons:

[0110] Examples of the skeleton represented by formula (A-6b-1) or formula (A-6b-2) include the following skeletons:

[0111] Examples of the skeleton represented by formula (A-6c) include the following skeletons:

[0112] Examples of the skeleton represented by formula (A-6d) include the following skeletons:

[0113] Examples of the skeleton represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following skeletons.

[0114] Examples of the skeleton represented by formula (A-8a-1) or formula (A-8a-2) include the following skeletons:

[0115] Examples of the skeleton represented by formula (A-8b) include the following skeletons:

[0116] Examples of the skeleton represented by formula (A-8c) include the following skeletons:

[0117] Examples of the skeleton represented by formula (A-8d) include the following skeletons:

[0118] Examples of the skeleton represented by formula (A-8e) include the following skeletons:

[0119] Examples of the skeleton represented by formula (A-8f) include the following skeletons:

[0120] Examples of the skeleton represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0121] Examples of other skeletons besides the phenol skeleton include the following skeletons.

[0122] Furthermore, the H of NH in the skeleton having an aromatic ring, the H of a hydroxy group bonded to the aromatic ring in the skeleton having an aromatic ring, and the hydrogen atom bonded to the aromatic ring in the skeleton having an aromatic ring may be substituted with a substituent. Examples of the substituent include the substituents (S) represented by the following formulae (S1) to (S7).

[0123] (In formulas (S1) to (S7), R ｓａ represents a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｂ R each independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｃ R each independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｄ ａｌｋｙｎｙｌ each independently represents an alkynyl group having 2 to 4 carbon atoms. ｓａ each independently represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓｂ each independently represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓａ and X ｓｂ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or X ｓａ and X ｓｂtogether with the carbon atom bonded to the hydroxy group, form a carbonyl group. n represents an integer of 0 to 5. * represents a bond.

[0124] <R ｓａ > R ｓａ Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms in the formula (I) include an alkyl group having 1 to 10 carbon atoms and a monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated.

[0125] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃ In the formula, examples of the divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkylene group having 1 to 10 carbon atoms and a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated. R ｓｂ , and R ｓｃ Examples of the group include the following groups: (* represents a bond.)

[0126] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌrepresents an alkynyl group having 2 to 4 carbon atoms. Examples of the alkynyl group having 2 to 4 carbon atoms include an ethynyl group, a 1-propynyl group, and a propargyl group (2-propynyl group).

[0127] <Ar ｓａ > Ar ｓａ The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0128] <Ar ｓｂ > Ar ｓｂ The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0129] <X ｓａ and X ｓｂ > X ｓａ and X ｓｂ In the formula (I), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms. A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0130] Examples of the substituent represented by formula (S1) include the following groups. (* represents a bond.)

[0131] Examples of the substituent represented by formula (S2) include the following groups. (* represents a bond.)

[0132] Examples of the substituent represented by formula (S3) include the following groups. (* represents a bond.)

[0133] Examples of the substituent represented by formula (S4) include the following groups. (* represents a bond.)

[0134] Examples of the substituent represented by formula (S5) include the following groups. (* represents a bond.)

[0135] Examples of the substituent represented by formula (S6) include the following groups. (* represents a bond.)

[0136] Examples of the substituent represented by formula (S7) include the following groups. (* represents a bond.)

[0137] Examples of other substituents include the following groups: (* represents a bond.)

[0138] The unit structure (A) is preferably at least one selected from the following: Note that the positions of the two bonds shown in each unit structure shown below are shown merely for convenience, and each bond can extend from any possible carbon atom, and the positions are not limited thereto.

[0139] (Examples of unit structures composed of aromatic amine skeletons) -NH- can also have a structure in which the hydrogen atom on the N is substituted.

[0140]

[0141] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0142] (Example of a unit structure composed of a phenol skeleton)

[0143] <B-1: Unit structure (B)> The unit structure (B) has one or more carbon atoms. The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The unit structure (B) is one or more types of unit structures containing a linking carbon atom bonding to an aromatic ring in the unit structure (A) [see (I-1) above], and includes, for example, a structure represented by the formula (B1), (B2), or (B3) shown below. The unit structure (B) can link two unit structures (A) by forming a covalent bond with the unit structure (A).

[0144] <<B-2: Formula (B1)>> The unit structure (B) includes, for example, a structure represented by the following formula (B1): The unit structure (B) may be a structure represented by the following formula (B1). In formula (B1), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched, or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. * represents a bond.

[0145] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a group in which H in a hydroxy group has been substituted with the above-mentioned substituent (S), and a halo group.

[0146] Furthermore, the two bonds in formula (B1) can be covalently bonded to the aromatic rings in the two structural units (A), respectively.

[0147] In the definitions of R and R' in formula (B1), the "aromatic ring" and "heterocycle" can be seen in (I-3) and (I-4) above.

[0148] In the definition of R and R′ in formula (B1), examples of the “alkyl group” include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1- Ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group ethyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,Examples include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0149] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0150] Examples of the ring structure formed by R and R' together with the carbon atoms to which they are bonded include structures represented by the following formulas. (In the formula, each Ar independently represents a residue of an aromatic ring. The carbon atom marked with * is the carbon atom bonded to R and R′ in formula (B1).)

[0151] Examples of the aromatic ring of Ar include aromatic rings represented by formula (G1).

[0152] The unit structure (B) containing the structure represented by formula (B1) is derived from, for example, an aldehyde compound or a ketone compound. Examples of the aldehyde compound include the compound represented by the following formula (B-1a). Examples of the ketone compound include the compound represented by the following formula (B-1b). (In formula (B-1a) and formula (B-1b), R and R' have the same meanings as R and R' in formula (B1), respectively, with the proviso that R is other than a hydrogen atom. In formula (B-1b), R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded.)

[0153] For example, in obtaining resin (G), the carbonyl groups in formula (B-1a) and formula (B-1b) are converted to *-C-* in formula (B1).

[0154] Some specific examples of the unit structure (B) containing the structure represented by formula (B1) are as follows. * basically indicates the bonding site with the unit structure (A). Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0155]

[0156] <<B-3: Formula (B2)>> The unit structure (B) includes, for example, a structure represented by the following formula (B2): The unit structure (B) may be a structure represented by the following formula (B2).

[0157] In formula (B2), Z ０ represents an aromatic ring residue or aliphatic ring residue having 6 to 30 carbon atoms, which may have a substituent, or an organic group in which two aromatic or aliphatic rings are linked by a single bond. Examples of the organic group in which two aromatic or aliphatic rings are linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and bicyclohexyl.

[0158] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a group in which H in a hydroxy group has been substituted with the above-mentioned substituent (S), and a halo group.

[0159] J １ and J ２ each independently represents a divalent organic group which may have a direct bond or a substituent. The divalent organic group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an aryl group (e.g., a phenyl group, a substituted phenyl group), or a halo group (e.g., fluorine) as a substituent. Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0160] The unit structure (B) containing the structure represented by formula (B2) is derived from, for example, a compound having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a compound having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group, or a compound having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0161] Examples of compounds having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom include compounds represented by the following formula (B-2a): Compounds having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (such as the benzylic carbon atom) of an alkylaryl group include compounds represented by the following formula (B-2b): Compounds having two carbon-carbon double bonds include compounds represented by the following formula (B-2c) or (B-2d): (In formula (B-2a), formula (B-2b), and formula (B-2b), J １ , J ２ , and Z ０ is J in formula (B2) １ , J ２ , and Z ０ In formula (B-2a), X ａ , and X ｂ each independently represents a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom. ａ , and Y ｂ each independently represents a hydroxyl group, an alkoxy group, or a halo group bonded to the α-position carbon atom (e.g., the benzyl-position carbon atom) of the alkylaryl group. In formula (B-2d), n represents an integer of 0 to 4.

[0162] For example, when obtaining resin (G), X in formula (B-2a) ａ -J １ is *-J in formula (B2). １ It is converted into ２ -X ｂ is J in formula (B2) ２For example, when resin (G) is obtained, Y in formula (B-2b) is converted to -*. ａ -J １ is *-J in formula (B2). １ It is converted into ２ -Y ｂ is J in formula (B2) ２ It is converted to -*.

[0163] An example of formula (B-2a) is the following compound:

[0164] An example of formula (B-2b) is the following compound:

[0165] An example of formula (B-2c) is the following compound:

[0166] Some specific examples of unit structures containing the structure represented by formula (B2) are as follows: * indicates the bonding site with unit structure A. Needless to say, the unit structure may contain the exemplified structure as a part of the whole.

[0167]

[0168] <<B-4: Formula (B3)>> In formula (B3), Z is a group having a monocyclic ring or a bicyclic, tricyclic, or tetracyclic fused ring, which may have a substituent, and which has 4 to 25 carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the monocyclic ring or the bicyclic, tricyclic, or tetracyclic fused ring excluding the substituent, and does not include the number of heteroatoms constituting the heterocyclic ring when the monocyclic ring or the fused ring is a heterocyclic ring.

[0169] The monocycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more) (hereinafter, may be referred to as a "non-Hückel monocycle"); at least one of the monocycles constituting the bicycle, tricycle, and tetracycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more), and the remaining monocycles may be either a monocycle having a π electron number that satisfies 4n+2 (n is an integer of 0 or more) or a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more).

[0170] The monocyclic or bicyclic, tricyclic, or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or higher fused ring, and the pentacyclic or higher fused ring preferably has 40 or less carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the pentacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the pentacyclic or higher fused ring is a heterocyclic ring.

[0171] X and Y may be the same or different and each represent -CR ３１ R ３２ represents a - group, and R ３１ and R ３２ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0172] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1.

[0173] In formula (B3), and in formula (B3) At least one of the above is bonded to any carbon atom constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0).

[0174] For example, in formula (B3), is bonded to any carbon atom constituting the non-Hückel monocyclic ring of Z (referred to as "carbon atom 1") (when x = 1) or extends from carbon atom 1 (when x = 0),

[0175] In formula (B3), is bonded to any of the carbon atoms (referred to as "carbon atom 2") constituting the non-Hückel monocycle of Z (when y = 1) or extends from carbon atom 2 (when y = 0), and carbon atom 1 and carbon atom 2 may be the same or different, and if they are different, they may belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0176] Furthermore, formula (B3) may optionally contain linking carbon atoms other than carbon atom 1 and carbon atom 2. When Z is a tricyclic or higher fused ring, the permutation position relationship between one or two non-Hückel monocycles to which carbon atoms 1 and 2 in formula (B3) belong and the remaining monocycles in the fused ring is arbitrary, and when carbon atom 1 and carbon atom 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2," respectively), the permutation position relationship between non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary. Some specific examples of organic groups containing a structure represented by formula (B3) are as follows. The bonding site with unit structure A is not particularly limited. Needless to say, a structure containing the exemplified structure as a part of the whole may also be used.

[0177] Examples include those having more than two bonds (*), but these excess bonds can be used for bonding to an aromatic ring in another polymer chain, for crosslinking, or for other purposes, or they can be bonds to hydrogen bonds.

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184] Hereinafter, in formula (B3), and in formula (B3) In this case, only one of the carbon atoms constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") is bonded (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0). As a more specific structure of formula (B3) in this case, for example, in the following formula (C31), p and k which can be bonding hands are １ and k ２ Among them, p and k １ , or p and k２ The remaining bond is bonded to a hydrogen atom.

[0185] In addition, in the following formula (C32), p and k which can be bonding hands １ , k ２ and m, p and k １ , p and k ２ , or depending on p and m, it can be a unit structure (B) represented by formula (B3). The remaining bond is bonded to a hydrogen atom.

[0186] Some specific examples of formula (B3) corresponding to formula (31) or formula (32) are as follows: * indicates the bonding site with the unit structure (A).

[0187] In formula (B3), a bond extends from the aromatic ring in each of these structures to another unit structure (for example, unit structure (A)), but in the specific examples below, such a bond is omitted. Needless to say, the unit structure may include the exemplified structure as a part of the whole. In the above specific examples, when there is no bond from the aromatic ring, it can be a specific example of a polymer terminal.

[0188] The novolak resin having the structure represented by formula (AB) can be prepared by a known method. For example, a compound having a ring represented by H-A-H and OHC-B, O═C-B, RO-B-OR, RO-CH ２ -B-CH ２ It can be prepared by condensing an oxygen-containing compound represented by —OR, etc. In the formula, A and B are as defined above, and R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0189] From the viewpoint of suitably achieving the effects of the present invention, the organic polymer preferably has a composite unit structure represented by any one of the following formulas (G-1), (G-2), (G-3-1), and (G-3-2). These composite unit structures are examples of the composite unit structure possessed by the resin (G). (In formulas (G-1), (G-2), (G-3-1) and (G-3-2), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２ R each independently represents an aromatic ring. １０１ , R １０２ , R １１１ , R １１２ , R １２１ , R １２２ , R １２４ , R １３１ , and R １３２ R each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 80 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, a sulfide bond, a sulfonyl group, a carboxyl group, or an ester bond. １０３ , R １１３ , R １２３ , and R １３３ are each independently 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 alkynyl 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. １０１ , n １０２ , n１１１ , n １１２ , n １２１ , n １２２ , n １３１ , and n １３２ Each of n independently represents 0 or an integer up to the maximum number that can be substituted on an aromatic ring. １２４ represents 0 or 1.)

[0190] Specific examples and suitable examples of R and R′ in formula (G-1), formula (G-2), formula (G-3-1), and formula (G-3-2) include the specific examples and suitable examples given in the description of R and R′ in formula (B-1), respectively.

[0191] From the viewpoint of preferably obtaining the effects of the present invention, Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２ Preferably, each independently represents a benzene ring or a naphthalene ring.

[0192] From the viewpoint of suitably achieving the effects of the present invention, it is preferred that in formulas (G-1), (G-2), (G-3-1), and (G-3-2), at least one of R and R' each independently represents an aromatic ring having 6 to 30 carbon atoms which may have a substituent, or that R and R' together with the carbon atom to which they are bonded represent a structure having a ring structure, and that the ring structure has an aromatic ring.

[0193] Examples of the composite unit structure include the following composite unit structures.

[0194] Examples of resin (G) include the following polymers: - Polymers described in claim 1 of WO 2010 / 147155 - Polymers described in claim 1 of WO 2013 / 047516 - Polymers described in claim 1 of WO 2013 / 146670 - Polymers described in claim 1 of WO 2023 / 162653 The contents of these publications are incorporated herein by reference to the same extent as if expressly set forth in their entirety.

[0195] The weight average molecular weight of the organic polymer is not particularly limited, but is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0196] The content of the organic polymer in the organic film-forming composition is not particularly limited, but is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and particularly preferably 70% by mass to 100% by mass, based on the film-forming components. The film-forming components refer to the components in the organic film-forming composition other than the solvent.

[0197] <Solvent> The solvent used in the organic film-forming composition is not particularly limited, but organic solvents generally used in chemical solutions for semiconductor lithography processes are preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexane, cyclohexane-1, cyclohexane-2, cyclohexane-3, cyclohexane-4, cyclohexane-5, cyclohexane-6, cyclohexane-7, cyclohexane-8, cyclohexane-9, cyclohexane-10, cyclohexane-11, cyclohexane-12, cyclohexane-13, cyclohexane-14, cyclohexane-15, cyclohexane-16, cyclohexane-17, cyclohexane-18, cyclohexane-19, cyclohexane-20, cyclohexane-21, cyclohexane-22, cyclohexane-23, cyclohexane-24, cyclohexane-25, cyclohexane-26, cyclohexane-27, cyclohexane-28, cyclohexane-29, cyclohexane-30, cyclohexane-31, cyclohexane-32, cyclohexane-33, cyclohexane-34, cyclohexane-35, cyclohexane-36, cyclohexane-37, cyclohexane-38, cyclohexane-49, cyclohexane-49, cyclohexane-51, cyclohexane-52, cyclohexane-53, cyclohexane-16, cyclohexane-18, cyclohexane-19, cyclohexane-29, cyclohexane-19, cyclohexane-29, cyclohexane-38, cyclohexane-19, Examples of suitable solvents include heptanone, 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 may be used alone or in combination of two or more.

[0198] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being particularly preferred.

[0199] The solvent preferably does not contain water. In other words, the organic film-forming composition preferably does not contain water. The content of water in the organic film-forming composition is not particularly limited, but is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and particularly preferably 0% by mass to 3% by mass.

[0200] The content of the solvent in the organic film-forming composition is not particularly limited, but is preferably 80% by mass to 99.99% by mass, more preferably 85% by mass to 99.9% by mass, and particularly preferably 90% by mass to 99% by mass. In other words, the content of the film-forming component in the organic film-forming composition is not particularly limited, but is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

[0201] <Crosslinking Agent> The organic film-forming composition may contain a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent has a structure different from that of the organic polymer.

[0202] Preferred crosslinking agents are aminoplast crosslinking agents and phenoplast crosslinking agents. Aminoplast crosslinking agents are addition condensation products of a compound having an amino group, such as melamine or guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensation products of a compound having a phenolic hydroxy group with formaldehyde.

[0203] Examples of the crosslinking agent include compounds having two or more of the following structures: (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0204] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0205] As the crosslinking agent, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group is preferred. These may be used alone or in combination of two or more.

[0206] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0207] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0208] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0209] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0210] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0211] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0212] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0213] (In formula (3d), R １ represents a methyl group or an ethyl group.)

[0214] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0215] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0216] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. １ is 1≦n １ an integer ≦3, n ２ is 2≦n ２ n is an integer ≦5 ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n ５ an integer ≦3, n ６ is 1≦n ６ an integer ≦4, n ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0217] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ n is an integer ≦5１１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ an integer ≦4, n １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0218] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0219] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0220] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0221] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 500 or less.

[0222] When the composition for forming an organic film contains a crosslinking agent, the content of the crosslinking agent in the composition for forming an organic film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, relative to the organic polymer.

[0223] <Curing Catalyst> The curing catalyst contained as an optional component in the organic film-forming composition may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0224] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0225] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0226] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0227] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0228] The curing catalyst may be used alone or in combination of two or more.

[0229] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass, relative to the crosslinking agent.

[0230] <Other Components> A surfactant may be further added to the organic film-forming composition in order to prevent pinholes, striations, etc., and to further improve the coating properties for preventing surface unevenness.

[0231] Examples of surfactants 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 octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0% by mass or less, and preferably 1.0% by mass or less, based on the total solid content of the organic film-forming composition. These surfactants may be added alone or in combination of two or more.

[0232] The organic film-forming composition may contain a polymer other than the organic polymer having a glass transition temperature of 150° C. or higher, as long as the effect of the present invention is not impaired. Such a polymer is not particularly limited.

[0233] (Method for manufacturing a semiconductor element) An example of a method for manufacturing a semiconductor element of the present invention includes an irradiation step, a resist pattern formation step, an organic film formation step, and an organic film removal step. The example of the method for manufacturing a semiconductor element may include other steps.

[0234] <Irradiation Step> The irradiation step is a step of irradiating the metal-containing resist film with light or an electron beam.

[0235] The metal-containing resist film is not particularly limited, but preferably contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0236] The metal-containing resist film is formed, for example, from a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP 2019-113855 A. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP 2019-532489 A. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738. Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0237] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0238] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0239] The film thickness of the metal-containing resist film is, for example, 5 nm to 10,000 nm, or 5 nm to 1,000 nm, or 5 nm to 40 nm.

[0240] The metal-containing resist film is formed on, for example, a substrate, a resist underlayer film, or the like.

[0241] Examples of the substrate include substrates used in the manufacture of precision integrated circuit elements, such as semiconductor substrates such as silicon wafers coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low-dielectric-constant materials (low-k materials), and flexible substrates.

[0242] The resist underlayer film is not particularly limited, and for example, a known resist underlayer film can be used. Examples of the resist underlayer film include an organic underlayer film and a silicon-containing resist underlayer film.

[0243] The resist film may be formed directly on the substrate, or may be formed on the resist underlayer film of the substrate on which the resist underlayer film has been formed. The resist underlayer film may be a single layer or multiple layers. For example, a two-layer resist underlayer film may be present between the substrate and the resist film. An example of a two-layer resist underlayer film is a two-layer resist underlayer film consisting of an organic underlayer film and a silicon-containing resist underlayer film.

[0244] The film thickness of the resist underlayer film is, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.

[0245] The light or electron beam irradiated onto the metal-containing resist film may be, for example, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F ２ Examples include excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), and electron beam.

[0246] The amount of light or electron beam irradiated onto the metal-containing resist film is not particularly limited.

[0247] After irradiation, post-exposure baking may be carried out as necessary, for example, at a heating temperature of 70° C. to 250° C. for a heating time of 0.3 to 10 minutes.

[0248] <Resist Pattern Forming Step> The resist pattern forming step is a step of bringing a developer into contact with the metal-containing resist film that has been irradiated with light or an electron beam, to obtain a resist pattern.

[0249] An organic solvent can be used as the developer, and development is carried out with the developer (solvent) after irradiation with light or electron beams. As a result, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed areas is removed, and a pattern of the metal-containing resist film is formed.

[0250] Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether teracetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, formic acid Ethyl, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate,Examples include propyl-3-methoxypropionate. Furthermore, surfactants and the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5°C to 50°C and a development time of 10 seconds to 600 seconds.

[0251] Examples of development methods using a developer include spin development using spin coating. The rotation speed during spin development is not particularly limited, but may be, for example, 500 rpm (rotations per minute) to 1500 rpm. The time for spin development is not particularly limited, but may be, for example, 30 seconds to 120 seconds.

[0252] In the resist pattern formation process, development is carried out so as not to dry the resist pattern in contact with the developer. Generally, in resist pattern formation, drying is carried out to remove the developer after development, but in the present invention, drying of the developer is not carried out. This is because drying of the developer would cause the resist pattern to collapse. For example, when development is carried out by spin development, spin drying is generally carried out after spin development, but in the present invention, spin drying is not carried out. After spin development, the organic film formation process is carried out without spin drying. Note that, generally, the rotation speed during spin drying is not particularly limited, but examples include 2000 rpm to 3000 rpm. The spin drying time is not particularly limited, but examples include 10 seconds to 90 seconds.

[0253] <Organic Film Forming Step> The organic film forming step is a step of applying the organic film forming composition of the present invention onto a resist pattern without drying the resist pattern in contact with the developer, thereby forming an organic film between the resist patterns.

[0254] The method for forming the organic film is not particularly limited, but for example, spin coating can be used. The rotation speed during spin coating is not particularly limited, but for example, 500 rpm to 1500 rpm can be used. The time for spin coating is not particularly limited, but for example, 30 seconds to 120 seconds can be used.

[0255] The organic film formed by the organic film forming step may be formed only between the resist patterns, or the organic film may be formed on the resist patterns in addition to between the resist patterns.

[0256] The thickness of the organic film to be formed is not particularly limited and is set to an appropriate thickness depending on the thickness of the metal-containing resist film, for example, in the range of 0.5 to 1.5 times the thickness of the metal-containing resist film.

[0257] <Organic Film Removal Step> The organic film removal step is not particularly limited as long as it can remove the organic film. Examples of methods for removing the organic film include dry etching, wet etching (e.g., decomposition and removal using an acidic solution), radiation etching, high-temperature baking, dissolution and removal using a solvent, and ozone treatment. These methods can be used alone or in combination of two or more. Examples of the temperature in the high-temperature baking include 200°C to 300°C. Examples of the baking time in the high-temperature baking include 1 minute or more. Examples of the atmosphere in the high-temperature baking include air. Examples of the solvent used for dissolution and removal using a solvent include the organic solvents listed in the description of the developer (organic solvent) used in the resist pattern formation step described above.

[0258] The gas used for dry etching is, for example, tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, dichloroborane, etc. These can be used alone or in combination of two or more.

[0259] Radiation etching is performed, for example, by irradiating ultraviolet rays in the presence of oxygen (e.g., in the atmosphere) or in the presence of an inert gas (e.g., nitrogen). In radiation etching, the organic film is decomposed and removed by the ultraviolet rays. Alternatively, in radiation etching, ozone is generated by irradiation with ultraviolet rays (e.g., 100 nm to 400 nm, 185 nm ultraviolet rays). Furthermore, when ultraviolet rays (e.g., 254 nm) are absorbed by ozone, active oxygen is generated. The organic film is then decomposed by the active oxygen. As a result, the organic film is removed.

[0260] In the organic film removal step, it is preferable that the organic film is selectively removed. In this respect, the etching rate of the organic film when removing the organic film is preferably at least twice, more preferably at least 10 times, and particularly preferably at least 20 times, the etching rate of the metal-containing resist film. The upper limit of the etching rate is not particularly limited, but, for example, the etching rate of the organic film when removing the organic film is not more than 100 times the etching rate of the metal-containing resist film.

[0261] In one example of a method for manufacturing a semiconductor device, the resist underlayer film (middle layer) is removed using the resist pattern of the metal-containing resist film (upper layer) thus formed as a protective film, then the organic underlayer film (lower layer) is removed using a film consisting of the patterned metal-containing resist film and the patterned resist underlayer film (middle layer) as a protective film, and finally, the substrate is processed using the patterned resist underlayer film (middle layer) and the patterned organic underlayer film (lower layer) as protective films.

[0262] The removal (patterning) of the resist underlayer film (middle layer) is performed by dry etching using the pattern of the metal-containing resist film (upper layer) as a protective film. ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８Gases such as fluorine, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the resist underlayer film. Metal-containing resist films are generally difficult to remove by dry etching with a halogen-based gas. In contrast, resist underlayer films containing a large amount of silicon atoms are quickly removed by a halogen-based gas. Therefore, it is possible to suppress a decrease in the film thickness of the metal-containing resist film that accompanies dry etching of the resist underlayer film. As a result, it becomes possible to use a thin metal-containing resist film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the resist underlayer film. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like, but are not limited to these.

[0263] When an organic underlayer film is present between the substrate and the resist underlayer film, the subsequent removal (patterning) of the organic underlayer film (lower layer) using the patterned resist underlayer film (intermediate layer) (and the patterned metal-containing resist film (upper layer), if any remains) as a protective film is preferably carried out by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film of the present invention, which contains a large number of silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0264] Thereafter, the (semiconductor) substrate is processed (patterned) using the patterned resist underlayer film (intermediate layer) and, if desired, the patterned organic underlayer film (underlayer) as protective films, preferably by dry etching using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ４), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ ) etc.

[0265] After removing (patterning) the organic underlayer film or after processing (patterning) the substrate, the resist underlayer film can be removed. The removal of the resist underlayer film can be carried out by dry etching or wet etching (wet method). Dry etching of the resist underlayer film is preferably carried out with a fluorine-based gas, as mentioned in the patterning, such as tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like, but are not limited to these.

[0266] The chemicals used for wet etching of the resist underlayer film include diluted hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH ４Examples of suitable alkaline solutions include an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). Examples of alkaline solutions include the aforementioned ammonia hydrogen peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicyclondecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These chemical solutions can also be used in combination.

[0267] In addition, an organic antireflective coating can be formed on the resist underlayer coating before the formation of the metal-containing resist film. The antireflective coating composition used therein is not particularly limited, and can be arbitrarily selected from those conventionally used in lithography processes. The antireflective coating can be formed by a conventional method, such as coating with a spinner or coater and baking.

[0268] Furthermore, the substrate onto which the silicon-containing resist underlayer film-forming composition for forming the silicon-containing resist underlayer film is applied may have an organic or inorganic antireflective film formed on its surface by a CVD method or the like, and the resist underlayer film may be formed thereon. Even in the case where an organic underlayer film is formed on a substrate and then a silicon-containing resist underlayer film is formed thereon, the substrate used may have an organic or inorganic antireflective film formed on its surface by a CVD method or the like.

[0269] The resist underlayer film formed from the composition for forming a silicon-containing resist underlayer film may also absorb light depending on the wavelength of the light used in the lithography process. In such cases, it can function as an anti-reflection film that has the effect of preventing light reflected from the substrate. Furthermore, the resist underlayer film can also be used as a layer for preventing interaction between the substrate and the metal-containing resist film, a layer having the function of preventing the adverse effects on the substrate of materials used in the metal-containing resist film or substances generated during exposure of the metal-containing resist film, a layer having the function of preventing the diffusion of substances generated from the substrate during heating and baking into the metal-containing resist film, and a barrier layer for reducing the poisoning effect of the metal-containing resist film due to the dielectric layer of the semiconductor substrate.

[0270] In another example of the method for manufacturing a semiconductor element of the present invention, the organic film-forming composition may also serve as a developer. In this case, the method for manufacturing a semiconductor element includes an irradiation step, a resist pattern and organic film-forming step, and an organic film-removing step.

[0271] The irradiation step may be the same as the irradiation step described above. The organic film removal step may be the same as the organic film removal step described above.

[0272] The resist pattern and organic film forming process is a process that replaces the aforementioned resist pattern forming process and organic film forming process. In the resist pattern and organic film forming process, the organic film forming composition of the present invention is applied onto a metal-containing resist film that has been irradiated with light or an electron beam, and the metal-containing resist film is developed to obtain a resist pattern and form an organic film between the resist patterns. Therefore, in this example, no developer is used.

[0273] The organic film-forming composition contains, for example, a solvent capable of dissolving the unexposed metal-containing resist film. The organic film-forming composition is applied, for example, by spin coating. The rotation speed during spin coating is not particularly limited, but may be, for example, 500 rpm to 1500 rpm. The spin coating time is not particularly limited, but may be, for example, 30 seconds to 120 seconds.

[0274] (Substrate with Metal-Containing Resist Pattern, and Method for Producing Substrate with Metal-Containing Resist Pattern) The substrate with a metal-containing resist pattern of the present invention is a substrate with a metal-containing resist pattern in which the composition for forming an organic film of the present invention is applied onto a metal-containing resist pattern, and an organic film is embedded between the metal-containing resist patterns. The method for producing a substrate with a metal-containing resist pattern of the present invention includes the steps of applying the composition for forming an organic film of the present invention onto a metal-containing resist pattern and embedding an organic film between the metal-containing resist patterns.

[0275] The metal-containing resist pattern is a resist pattern formed from a metal-containing resist film. The metal-containing resist pattern can be formed, for example, by the above-mentioned <irradiation step> and <resist pattern formation step>. Examples of methods for forming an organic film include the coating methods mentioned in the above-mentioned <organic film formation step>. The metal-containing resist pattern is formed, for example, on a substrate, a resist underlayer film, etc.

[0276] An embodiment of a method for manufacturing a semiconductor device will be described below with reference to the drawings. FIGS. 1A to 1E are cross-sectional schematic diagrams illustrating one embodiment of the method for manufacturing a semiconductor device. This embodiment includes an irradiation step, a resist pattern formation step, an organic film formation step, and an organic film removal step. First, a substrate 1 is prepared ( FIG. 1A ). An organic underlayer film 2, a silicon-containing resist underlayer film 3, and a metal-containing resist film 4 are stacked on the substrate 1 in this order. Next, the metal-containing resist film 4 is irradiated with light L through a mask 10 ( FIG. 1B ). The light L is, for example, EUV light. Alternatively, electron beams may be used instead of light L. Next, a developer is brought into contact with the metal-containing resist film irradiated with light L, thereby obtaining a resist pattern 4A ( FIG. 1C ). Development is performed by spin development, without spin drying. Next, without spin drying, the organic film-forming composition of the present invention is applied to the resist pattern 4A, forming an organic film 5 between the resist pattern 4A ( FIG. 1D ). 1D, the organic film 5 may also be formed on the resist pattern 4A. Next, the organic film 5 is removed by etching (FIG. 1E). By doing so, a resist pattern in which pattern collapse is suppressed can be obtained.

[0277] As shown in FIG. 2, the organic film 5 between the resist patterns 4A may be present only between the resist patterns 4A, and may not be present on the resist patterns 4A.

[0278] Another embodiment of a method for manufacturing a semiconductor device will be described below with reference to the drawings. FIGS. 3A to 3D are cross-sectional schematic diagrams illustrating one embodiment of the method for manufacturing a semiconductor device. This embodiment includes an irradiation step, a resist pattern and organic film formation step, and an organic film removal step. The organic film-forming composition also serves as a developer. First, a substrate 1 is prepared ( FIG. 3A ). An organic underlayer film 2, a silicon-containing resist underlayer film 3, and a metal-containing resist film 4 are stacked on the substrate 1 in this order. Next, the metal-containing resist film 4 is irradiated with light L through a mask 10 ( FIG. 3B ). The light L is, for example, EUV light. Alternatively, electron beams may be used instead of light L. Next, the organic film-forming composition of the present invention is applied to the metal-containing resist film 4 irradiated with light L, and the metal-containing resist film 4 is developed to obtain a resist pattern 4A, and an organic film 5 is formed between the resist patterns 4A ( FIG. 3C ). The application is performed by spin coating. Next, the organic film 5 is removed by etching ( FIG. 3D ). By doing so, a resist pattern in which pattern collapse is suppressed can be obtained.

[0279] The present invention will be explained in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0280] In the examples, the apparatus and conditions used for analyzing the physical properties of samples are as follows. (1) Molecular Weight Measurement The molecular weight used in the present invention is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurement conditions are as follows. GPC apparatus: trade name HLC-8220GPC (manufactured by Tosoh Corporation) GPC column: trade name Shodex (registered trademark) KF803L, KF802, KF801 (manufactured by Showa Denko K.K.) Column temperature: 40°C Eluent (elution solvent): tetrahydrofuran Flow rate (flow rate): 1.0 mL / min Standard sample: polystyrene (manufactured by Showa Denko K.K.)

[0281] [1] Polymer Synthesis (Synthesis Example 1) N-phenyl-1-naphthylamine (8.00 g, 0.6 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxaldehyde (8.39 g, 0.036 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and paratoluenesulfonic acid monohydrate (0.7 g, 0.0036 mol, manufactured by Kanto Chemical Co., Ltd.) were added to a 100 mL four-neck flask, and 1,4-dioxane (213 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The mixture was heated to 110°C to dissolve the mixture and initiate polymerization. After 12 hours, the mixture was allowed to cool to room temperature and then reprecipitated in methanol (400 g, manufactured by Kanto Chemical Co., Ltd.). The resulting precipitate was filtered and dried in a vacuum dryer at 50°C for 10 hours and then at 120°C for 24 hours to obtain the target polymer. GPC analysis of the resulting polymer revealed that the weight average molecular weight Mw was 1,200. The obtained polymer can be represented by the following formula (E-1): 1.5 g of the obtained polymer was dissolved in 48.5 g of propylene glycol monomethyl ether to obtain a polymer solution.

[0282]

[0283] Synthesis Example 2 Under a nitrogen atmosphere, carbazole (8.0 g, 47.8 ml, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-naphthaldehyde (7.55 g, 48.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and paratoluenesulfonic acid monohydrate (0.95 g, 50.0 L, manufactured by Kanto Chemical Co., Ltd.) were placed in a 100 mL four-neck flask. 1,4-Dioxane (8 g, manufactured by Kanto Chemical Co., Ltd.) was then added, and the mixture was heated to 100°C with stirring, and a polymerization reaction was carried out for 4 hours. After completion of the reaction, the mixture was allowed to cool to 6°C, diluted with chloroform (40 g, manufactured by Kanto Chemical Co., Ltd.), and the resulting solution was added to methanol (200 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate the polymer. The resulting precipitate was filtered, dried in a vacuum dryer at 60°C for 10 hours, and then further dried at 120°C for 24 hours, yielding 10.03 g of the target polymer. The obtained polymer was subjected to GPC analysis and found to have a weight average molecular weight Mw of 3000. The obtained polymer can be represented by the following formula (E-2): 1.5 g of the obtained polymer was dissolved in 48.5 g of propylene glycol monomethyl ether to obtain a polymer solution.

[0284]

[0285] (Synthesis Example 3) 50.0 g of phenylindole, 46.7 g of 9-fluorenone, 12.5 g of methanesulfonic acid, and 109.1 g of propylene glycol monomethyl ether acetate were placed in a flask. The mixture was then heated to reflux under nitrogen and reacted for approximately 16 hours. After the reaction was stopped, the mixture was reprecipitated in methanol and dried to obtain a polymer. GPC analysis of the obtained polymer revealed that it had a weight average molecular weight Mw of 1,400. The obtained polymer can be represented by the following formula (E-3). 1.5 g of the obtained polymer was dissolved in 48.5 g of propylene glycol monomethyl ether to obtain a polymer solution.

[0286]

[0287] Comparative Synthesis Example 1: 40.0 g of EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), 20.3 g of 9-anthracenecarboxylic acid, and 13.7 g of benzoic acid were dissolved in 302.0 g of propylene glycol monomethyl ether in a two-neck flask, and then 1.5 g of benzyltriethylammonium was added and the mixture was refluxed for 24 hours to allow the reaction to proceed. 11 g of anion exchange resin and 11 g of cation exchange resin were added to the resulting solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. The ion exchange resin was separated, and a solution of a polymer represented by the following formula (E-4) was obtained. The weight average molecular weight Mw of the resulting resin, measured in terms of polystyrene by GPC, was 4,100.

[0288]

[0289] [2-1] O ２ Etching rate measurement ２ The etcher and etching gas used for measuring the etching rate were as follows: Etcher: RIE-10NR (manufactured by Samco) Etching gas: O ２The polymer solutions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were each applied onto a silicon wafer using a spinner. The solution was heated on a hot plate at 250°C for 1 minute to form a 50 nm thick film. Similarly, a tin oxide-based resist composition was applied to a silicon wafer using a spinner to form a resist film (film thickness 22 nm). For each of the coating film obtained from the polymer solution and the resist film obtained from the tin oxide-based resist composition, O was used as the etching gas. ２ The dry etching rates were measured using a gas, and the dry etching rates of the coating films prepared from the polymer solutions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were compared with the dry etching rate of the resist film obtained from the tin oxide-based resist composition. The results are shown in Table 1. The etch rates in Table 1 are etch rates relative to the etch rate of the resist film obtained from the tin oxide-based resist composition, which is set to 1.

[0290]

[0291] [2-2] Measurement of Glass Transition Temperature (Tg) The glass transition temperature was measured using the following differential scanning calorimeter under the following conditions: Differential scanning calorimeter: DSC Q2000 (manufactured by TA Instruments) Temperature range: room temperature to 350°C Heating rate: 5°C / min Heating rate: 5°C / min Atmosphere: nitrogen The endothermic onset temperature during the second heating was taken as the glass transition temperature. The endothermic onset temperature was determined as the intersection of the baseline up to the start of endothermic absorption and the tangent to the endothermic curve.

[0292] The polymer solutions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were each applied to a silicon wafer using a spinner. The wafer was heated on a hot plate at 100°C for 1 minute to remove the solvent, and the remaining polymer film was then scraped off to obtain a polymer powder. The obtained polymer powder was analyzed using a differential scanning calorimeter to measure the glass transition temperature. The results are shown in Table 2.

[0293]

[0294] [3] Preparation of Organic Underlayer Film Forming Composition Under nitrogen, carbazole (6.69 g), 9-fluorenone (7.28 g), and paratoluenesulfonic acid monohydrate (0.76 g) were added to a 100 ml four-neck flask. 1,4-dioxane (6.69 g) was then added and stirred. The mixture was heated to 100°C to dissolve the mixture and initiate polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g), and the diluted mixture was added to methanol (168 g) to precipitate the mixture. The resulting precipitate was collected by filtration, and the collected solid was dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (T) (hereinafter referred to as PCzFL). The weight-average molecular weight (Mw) of PCzFL, measured in terms of polystyrene equivalent by GPC, was 2,800, and the polydispersity (Mw / Mn) was 1.77.

[0295]

[0296] 20 g of PCzFL, 3.0 g of tetramethoxymethylglycoluril (trade name Powder Link 1174, manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)) as a crosslinking agent, 0.30 g of pyridinium paratoluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (trade name, manufactured by DIC Corporation) as a surfactant were mixed, and the resulting mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to form a solution. The resulting solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and further filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an organic underlayer film.

[0297] [4] Preparation of Resist Underlayer Film Forming Composition 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane, and 62.1 g of propylene glycol monoethyl ether were placed in a 300 ml flask, and 8.4 g of 0.2 M aqueous nitric acid solution was added dropwise to the resulting mixed solution while stirring with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. The reaction by-products, ethanol and water, were then removed by vacuum distillation, and the resulting solution was concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 10 mass percent, calculated as a 100% propylene glycol monoethyl ether solvent ratio and solid residue at 150°C, and the solution was filtered through a nylon filter (pore size 0.1 μm). The resulting polysiloxane polymer contained a structure represented by the following formula (U), and its weight-average molecular weight, measured as polystyrene equivalent by GPC, was Mw 2,400.

[0298]

[0299] The obtained polysiloxane polymer solution (solid content 10% by mass) (4.9 g), maleic acid (0.005 g), triphenylsulfonium nitrate (0.005 g), and propylene glycol monoethyl ether (195 g) were mixed and filtered through a 0.1 μm fluororesin filter to prepare a composition for forming a resist underlayer film.

[0300] [5-1] Example 1 <Formation of Resist Pattern> The organic underlayer film-forming composition described above was spin-coated onto a silicon wafer and heated on a hot plate at 215°C for 1 minute to form an organic underlayer film (layer A) (film thickness 90 nm). The resist underlayer film-forming composition described above was spin-coated thereon and heated on a hot plate at 215°C for 1 minute to form a resist underlayer film (layer B) (film thickness 10 nm). A resist solution (tin oxide-based resist) was further spin-coated thereon and heated at 130°C for 1 minute to form an EUV resist layer (layer C), which was then exposed using an EB exposure system (ELS-G130) manufactured by Elionix. Note that the exposure was performed so that the resist line width after development described below would be 16 nm and the line width (space width) would be 28 nm. After exposure, post-exposure baking (PEB, 180°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Then, spin development was performed at 1000 rpm for 60 seconds using an organic solvent (propylene glycol monomethyl ether acetate) as a developer. Thereafter, without spin drying, the polymer solution prepared in Synthesis Example 1 was applied, and the propylene glycol monomethyl ether acetate used for development was replaced with this solution. The silicon substrate was then spun at 1500 rpm for 60 seconds to dry the solvent in the solution, and then heated at 250°C for 60 seconds to form a coating film, which allowed the resist pattern to be embedded. The formed coating film was then subjected to O ２ (flow rate 10 sccm) and N ２ The resist was removed by dry etching using a mixed gas (flow rate 20 sccm) to obtain a resist pattern.

[0301] [5-2] Example 2 <Formation of Resist Pattern> A resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Synthesis Example 2.

[0302] [5-3] Example 3 <Formation of Resist Pattern> A resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Synthesis Example 3.

[0303] [5-4] Comparative Example 1 <Formation of Resist Pattern> The organic underlayer film-forming composition described above was spin-coated onto a silicon wafer and heated on a hot plate at 215°C for 1 minute to form an organic underlayer film (layer A) (film thickness 90 nm). The resist underlayer film-forming composition described above was spin-coated thereon and heated on a hot plate at 215°C for 1 minute to form a resist underlayer film (layer B) (film thickness 10 nm). A resist solution (tin oxide-based resist) was further spin-coated thereon and heated at 130°C for 1 minute to form an EUV resist layer (layer C), which was then exposed using an EB exposure system (ELS-G130) manufactured by Elionix. Note that the exposure was performed so that the resist line width after development described below would be 16 nm and the line width (space width) would be 28 nm. After exposure, the resist was subjected to post-exposure baking (PEB, 180°C for 1 minute), cooled to room temperature on a cooling plate, and spin-developed at 1000 rpm for 60 seconds using an organic solvent (propylene glycol monomethyl ether acetate) as a developer, followed by spin-drying at 2500 rpm for 30 seconds to remove the developer, yielding a resist pattern.

[0304] [5-5] Comparative Example 2 <Formation of Resist Pattern> A resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Comparative Synthesis Example 1.

[0305] The pattern dimensions of the resist patterns obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured using a critical dimension SEM (CG4100) manufactured by Hitachi High-Tech Corporation. The results are shown in Table 3. In Table 3, "good" means that a pattern with a dimension of 16 nm was formed without peeling or bending. LWR (line width roughness) indicates the variation in pattern dimensions.

[0306]

[0307] As shown in Table 3, when a pattern is formed by embedding a pattern after development using a polymer solution having a glass transition temperature of 150°C or higher and then removing the resin by dry etching, peeling of the pattern during development is suppressed and a good fine pattern with little variation in pattern dimensions can be formed.

[0308] REFERENCE SIGNS LIST 1 substrate 2 organic underlayer film 3 silicon-containing resist underlayer film 4 metal-containing resist film 4A resist pattern 5 organic film 10 mask L light

Claims

1. A composition for forming an organic film used to form an organic film that is formed between resist patterns formed from a metal-containing resist film and is subsequently removed, the composition comprising an organic polymer having a glass transition temperature of 150°C or higher and a solvent.

2. The organic film-forming composition according to claim 1, wherein the metal-containing resist film contains at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

3. The organic film-forming composition according to claim 1, wherein the organic polymer has a glass transition temperature of 150°C to 350°C.

4. The organic film-forming composition according to claim 1, wherein the organic polymer is a resin (G) having a complex unit structure, the complex unit structure having a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms, and the resin is obtained by a reaction that forms a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B).

5. The organic film-forming composition according to claim 4, wherein the unit structure (A) has at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring.

6. The organic film-forming composition according to claim 4, wherein the unit structure (B) is a unit structure derived from an aldehyde compound or an aldehyde equivalent, and the aldehyde equivalent is an organic compound capable of forming a covalent bond with an aromatic ring, and is an organic compound having a ketone group; an acetal group; a ketal group; a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, an alkoxy group or a halo group bonded to the α-position carbon atom of an alkylaryl group; or a carbon-carbon unsaturated bond.

7. The organic film-forming composition according to claim 1, wherein the organic polymer has a composite unit structure represented by any one of the following formulas (G-1), (G-2), (G-3-1), and (G-3-2): (In formulas (G-1), (G-2), (G-3-1) and (G-3-2), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２ R each independently represents an aromatic ring. １０１ , R １０２ , R １１１ , R １１２ , R １２１ , R １２２ , R １２４ , R １３１ , and R １３２ R each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 80 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, a sulfide bond, a sulfonyl group, a carboxyl group, or an ester bond. １０３ , R １１３ , R １２３ , and R １３３ are each independently 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 alkynyl 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. １０１ , n １０２ , n １１１ , n １１２ , n １２１ , n １２２ , n １３１ , and n １３２ Each of n independently represents 0 or an integer up to the maximum number that can be substituted on an aromatic ring. １２４ represents 0 or 1.) 8. Ar １０１ , Ar １０２ , Ar １１１ , Ar １１２ , Ar １２１ , Ar １２２ , Ar １３１ , and Ar １３２ The organic film-forming composition according to claim 7 , wherein each independently represents a benzene ring or a naphthalene ring.

9. The composition for forming an organic film according to claim 7, wherein in formula (G-1), formula (G-2), formula (G-3-1), and formula (G-3-2), at least one of R and R' each independently represents an aromatic ring having 6 to 30 carbon atoms which may have a substituent, or R and R' together with the carbon atom to which they are bonded represent a structure having a ring structure, and the ring structure has an aromatic ring.

10. The organic film-forming composition according to claim 1, which is used to prevent the resist pattern from collapsing.

11. The organic film-forming composition according to claim 1, which also serves as a developer when forming the resist pattern.

12. A method for manufacturing a semiconductor device, comprising: a step of irradiating a metal-containing resist film with light or an electron beam; a step of contacting the metal-containing resist film irradiated with the light or electron beam with a developer to obtain a resist pattern; a step of applying an organic film-forming composition according to any one of claims 1 to 10 onto the resist pattern without drying the resist pattern in contact with the developer, thereby forming an organic film between the resist patterns; and a step of removing the organic film.

13. The method for manufacturing a semiconductor device according to claim 12, wherein in the step of forming the organic film, the organic film is also formed on the resist pattern.

14. The method for manufacturing a semiconductor device according to claim 12, wherein the step of removing the organic film is selected from the group consisting of dry etching, wet etching, radiation etching, high-temperature baking, dissolving and removing using a solvent, and ozone treatment.

15. A substrate with a metal-containing resist pattern, in which the organic film-forming composition according to any one of claims 1 to 10 is applied onto a metal-containing resist pattern, thereby embedding an organic film between the metal-containing resist patterns.

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