Wafer end part protection film formation composition for semiconductor manufacturing

Abstract

To provide a protection film formation composition capable of forming, with good film formability, a protection film having excellent dry etching resistance at an end part of a semiconductor manufacturing substrate (wafer) by a simple coating method in the manufacturing of a semiconductor device.SOLUTION: A wafer end part protection film formation composition for semiconductor manufacturing contains a rein (G) and a solvent, in which the rein (G) includes a composite unit structure. The composite unit structure includes a unit structure (A) having an aromatic ring, and a unit structure (B) having one or more carbon atms. The rein (G) is a resin that is obtained by a reaction for generating a covalent linkage between the carbon atom constructing the aromatic ring of the unit structure (A) and the carbon atom in the unit structure (B).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a protective film-forming composition for forming a protective film on an edge of a substrate (wafer) for semiconductor manufacturing in a semiconductor device manufacturing process, a protective film formed from the protective film-forming composition, a wafer for semiconductor manufacturing manufactured using the protective film, and a method for manufacturing the wafer for semiconductor manufacturing and a semiconductor device. [Background technology]

[0002] In the manufacture of semiconductor devices, as the manufacturing process becomes more complicated, a method of applying a chemical solution containing a metal to a wafer is being considered for the purpose of, for example, improving the etching selectivity. Furthermore, for example, in the case of performing exposure using extreme ultraviolet (EUV), the resolution of the resist pattern is increased, and since the resist has high etching resistance, it is being considered to form a resist film using a resist containing an inorganic metal. Meanwhile, adhesion of metal to unintended portions of a wafer in the manufacturing process of a semiconductor device greatly affects the electrical characteristics of the semiconductor device. However, when forming a coating film containing a metal as described above, the chemical solution supplied to the surface of the wafer may wrap around to the edge of the wafer (for example, the outer periphery (edge ​​portion, etc.) of the surface, the peripheral end surface (bevel portion, etc.), and the outer periphery of the back surface, etc.), and the coating film may be formed on the edge of the wafer at these unintended outer periphery and peripheral end surface, which may cause metal contamination of these portions. Furthermore, if the contaminated portion of the wafer comes into contact with a wafer processing device, such as an exposure device or an etching device, or a wafer transport mechanism, there is a risk that wafers that are transported and processed after the wafer in question via these processing devices or transport mechanisms will also become metal contaminated, i.e., cross-contamination will occur.

[0003] A technique has been disclosed for forming a coating film on the surface of a substrate such that the peripheral edge face or the outer periphery of the back surface side of the substrate does not come into contact with the coating film (Patent Document 1).

[0004] A method for manufacturing a semiconductor device in which peeling of a film from a bevel portion of a substrate is suppressed has been disclosed (Patent Document 2).

[0005] A method for forming a protective film on the peripheral edge of a substrate has been disclosed, the method comprising the steps of: (i) coating the peripheral edge of the substrate with a composition for forming a protective film, the composition including an aromatic ring-containing resin (A) having an organic group represented by a specific general formula (1) and a solvent; and (ii) curing the coated composition for forming a protective film by applying heat or light irradiation to form the protective film on the peripheral edge of the substrate (see Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2017-098333 A [Patent Document 2] JP 2011-228340 A [Patent Document 3] JP 2024-24828 A Summary of the Invention [Problem to be solved by the invention]

[0007] The problem that the present invention aims to solve is to provide a protective film-forming composition that can form a protective film having good dry etching resistance and good film-forming properties on the edge of a semiconductor manufacturing substrate (wafer) by a simple method of application in the manufacture of a semiconductor device, a protective film formed from the protective film-forming composition, a semiconductor manufacturing wafer manufactured using the protective film, and a method for manufacturing the semiconductor manufacturing wafer and the semiconductor device. [Means for solving the problem]

[0008] The present invention encompasses the following: [1] A composition comprising a resin (G) and a solvent, The resin (G) has a composite unit structure, the composite 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 for forming 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). A composition for forming a protective film on a wafer edge in semiconductor manufacturing. [2] The composition for forming a wafer edge protection film for semiconductor manufacturing according to [1], wherein the unit structure (A) has 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 bonded to the aromatic ring, or does not have a heteroatom as an atom constituting the aromatic ring or an atom bonded to the aromatic ring. [3] The composition for forming a wafer edge protection film for semiconductor manufacturing according to [1] or [2], wherein the unit structure (B) is a unit structure derived from an aldehyde compound or an aldehyde equivalent. [4] The composition for forming a wafer edge protection film for semiconductor manufacturing according to [3], wherein 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. [5] A protective film which is a cured product of a coating film made of the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [4]. [6] A semiconductor manufacturing wafer having a protected edge, the semiconductor manufacturing wafer having a protective film formed by applying a composition for forming a semiconductor manufacturing wafer edge protective film described in any one of [1] to [4] to the edge of a wafer precursor. [7] (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; (C) etching a semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: A process (X) of forming a protective film on an edge of a semiconductor manufacturing wafer using a composition for forming a protective film for a semiconductor manufacturing wafer according to any one of [1] to [4], A method for manufacturing a semiconductor device. [8] The method for manufacturing a semiconductor device according to [7], wherein the step (X) is carried out before the step (A). [9] The method for manufacturing a semiconductor device according to [7], wherein the step (X) is carried out between the step (A) and the step (B).

[10] The method for manufacturing a semiconductor device according to [7], wherein the step (X) is carried out after the step (B) or the step (C).

[11] The step (X) is carried out before the step (A), In the step (A), the resist film is formed on at least a portion of the protective film, A step (Y) of removing the resist film on the protective film; A method for manufacturing a semiconductor device according to [7].

[12] The method for manufacturing a semiconductor device according to any one of [7] to

[11] , further comprising a step (Z) of removing the protective film.

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

[11] or

[12] , further comprising, after the step (Y), a step (Z) of removing the protective film.

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

[12] , wherein the removal of the protective film in the step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning liquid.

[15] The method for manufacturing a semiconductor device according to

[13] , wherein the removal of the protective film in the step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning liquid.

[16] A method for manufacturing a semiconductor manufacturing wafer, comprising: A step of applying a composition for forming a wafer edge protection film for semiconductor production according to any one of [1] to [4] to an edge of a wafer precursor, and producing a wafer whose edge is protected by the formed protective film; A method for manufacturing a wafer for semiconductor manufacturing, comprising: Effect of the Invention

[0009] According to the present invention, a protective film having good dry etching resistance can be formed with good film forming properties on the edge of a substrate (wafer) for semiconductor manufacturing by a simple coating method. This makes it possible to prevent cross-contamination due to metal contamination, for example, in the subsequent semiconductor device manufacturing process, and improve the yield of non-defective semiconductor manufacturing equipment. [Brief description of the drawings]

[0010] [Figure 1A] FIG. 2 is a schematic diagram showing an example of an edge of a wafer to explain the edge of the wafer. [Figure 1B] FIG. 11 is a schematic diagram showing another example of the edge of the wafer to explain the edge of the wafer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] (Composition for forming a protective film on a wafer edge for semiconductor manufacturing) The composition for forming a protective film on a wafer edge for semiconductor manufacturing of the present invention (hereinafter, sometimes referred to as "composition for forming a protective film") is a composition for forming a protective film used to protect the edge of a wafer for semiconductor manufacturing. The composition for forming a protective film contains a resin (G) and a solvent.

[0012] <Resin (G)> The resin of the present invention is a resin (G) having a complex unit structure. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. Resin (G) is a resin obtained by a reaction forming a covalent bond between a carbon atom constituting the aromatic ring of unit structure (A) and a carbon atom in unit structure (B). In this specification, resin (G) may be referred to as a "novolak resin."

[0013] 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 the aromatic ring.

[0014] The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. An aldehyde equivalent is an organic compound capable of covalently bonding with an aromatic ring, and is an organic compound having a ketone group; an acetal group; a ketal group; a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl, alkoxy or halo group bonded to the alpha carbon atom of an alkylaryl group; or a carbon-carbon unsaturated bond.

[0015] [I. Definitions of Terms] In this specification, the 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.

[0016] (I-1) "Novolac resin" The term "novolac resin" is used in a broad sense to include not only phenol-formaldehyde resins (so-called novolac-type phenolic resins) and aniline-formaldehyde resins (so-called novolac-type 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 that can form a covalent bond with an aromatic ring [e.g., 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-position carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group; a carbon-carbon unsaturated bond such as divinylbenzene or dicyclopentadiene] and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring) in the presence of an acid catalyst or under reaction conditions equivalent thereto.

[0017] Therefore, the novolak resin referred to in this specification is a resin formed by linking a plurality of compounds having aromatic rings together, by 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.

[0018] In this specification, the terms unit structure (A) and unit structure (B) are used as 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).

[0019] (I-2) "Residue" The term "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 or polyvalent group. For example, if one hydrogen atom is replaced with one bond, it becomes a monovalent organic group, and if two hydrogen atoms are replaced with bonds, it becomes a divalent organic group.

[0020] (I-3) "Aromatic ring" (aromatic group, aryl group, arylene group) The term "aromatic ring" refers to a concept that includes aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof (sometimes called "aromatic groups," "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)), and includes not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocycle is an aromatic monocycle, but the remaining monocycles that form a condensed ring with the aromatic monocycle may be a monocyclic heterocycle (heteromonocycle) or a monocyclic alicyclic hydrocarbon (alicyclic monocycle). In this specification, a heteroaryl group is included in an aryl group, and a heteroarylene group is included in an arylene group.

[0021] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzoanthracene, 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, and 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 pyrrole. 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.

[0022] The aromatic ring (eg, benzene ring, naphthalene ring, etc.) may have an arbitrary substituent, and such substituents include, for example, the following atoms and groups. Halogen atoms - A saturated or unsaturated linear, branched or cyclic hydrocarbon group, the hydrocarbon chain of which may be interrupted one or more times by oxygen atoms (-R a ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), whose hydrocarbon chains may be interrupted one or more times by oxygen atoms, as well as aryl groups, etc.); -OR (where R is the hydrocarbon group -R a Represents.) Aryloxy group -NH2, -NHR or -NR2 (wherein the two R's may be the same or different), where R is the hydrocarbon group -R a Represents. Hydroxyl Hydroxyalkyl groups Carboxylic group Formyl group Cyano group Nitro group an ester group (e.g., -COR or -OCOR, where R is the hydrocarbon group -R a Represents.) an amide group [for example, -NHCOR, -CONHR, -NRCOR (wherein the two R's may be the same or different), or -CONR2 (wherein the two R's may be the same or different), where R is the hydrocarbon group -R a represents.] sulfonyl-containing groups (e.g., -SO2R, where R is the hydrocarbon group -R a Or a hydroxyl group -OH.) Thiol group (-SH) A sulfide-containing group (-SR, where R is the hydrocarbon group -R a Represents.) Organic groups containing ether bonds [R 11 -OR 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 following formula (I); for example, an organic group having an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group]

[0023] The "aromatic ring" further includes an organic group having one or more condensed rings of aromatic rings (such as benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocyclic rings. Examples of the aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene, and examples of the heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0024] 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 -SO2-. The divalent linking group may also be a divalent group obtained by removing one hydrogen atom from any of the substituents of the aromatic ring described above.

[0025] (I-4) "Heterocycle" The term "heterocycle" includes both aliphatic heterocycles and aromatic heterocycles, and is a concept that includes not only monocyclic (heteromonocycles) but also polycyclic (heteropolycycles). In the case of polycyclic, at least one monocycle is a heteromonocycle, but the remaining monocycles may be aromatic hydrocarbon monocycles or alicyclic monocycles. For aromatic heterocycles, see the examples in (I-3) above. As with the aromatic ring in (I-3), it may have a substituent.

[0026] (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 aromatic groups, 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 aromatic compounds). It may have a substituent, as with the aromatic ring of (I-3) above.

[0027] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0028] 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 an aromatic compound]. It includes non-aromatic bicyclic rings, non-aromatic tricyclic rings, and non-aromatic tetracyclic rings.

[0029] When the "non-aromatic ring" is a bicyclic ring, the "non-aromatic bicyclic ring" refers to a condensed ring composed of two monocyclic hydrocarbons that are not aromatic, typically a condensed ring of two alicyclic compounds. In this specification, it may also be referred to as an aliphatic bicyclic ring (which may include an aliphatic heterobicyclic ring, or may contain an unsaturated bond as long as it does not belong to an aromatic compound). Examples of non-aromatic bicyclic rings include bicyclopentane, bicyclooctane, and bicycloheptene.

[0030] When the "non-aromatic ring" is a tricyclic ring, the "non-aromatic tricyclic ring" refers to a condensed ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a condensed ring of three alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not aromatic). Examples of non-aromatic tricyclic rings include tricyclooctane, tricyclononane, and tricyclodecane.

[0031] When the "non-aromatic ring" is a tetracyclic ring, the "non-aromatic tetracyclic ring" refers to a condensed ring composed of four monocyclic hydrocarbons that are not aromatic, typically a condensed 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 aromatic). Examples of non-aromatic tetracyclic rings include hexadecahydropyrene.

[0032] (I-6) "The carbon atoms constituting the ring (portion)" means the carbon atoms constituting the hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring) in the state without substituents.

[0033] (I-7) "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.

[0034] (I-8) In the chemical structural formula showing the unit structure of the novolak resin in the present specification, a bond (* represented) may be described for convenience, but such a bond can take any bondable position in the unit structure and does not limit the bond position in the unit structure in any way without special description.

[0035] <<Resin (G)>> Resin (G) has a composite unit structure. Resin (G) may be a polymer. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0036] The composite unit structure possessed by resin (G) is represented by, for example, the following formula (AB).

Chemical formula

[0037] <<<A-1: Unit structure (A)>>> Unit structure (A) has an aromatic ring. The unit structure (A) may have, 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 directly bonded to an aromatic ring. The unit structure (A) may not have a heteroatom, for example, as an atom constituting the aromatic ring or an atom bonded to the aromatic ring.

[0038] 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.

[0039] Preferably, such an aromatic ring has 4 to 30, more preferably 4 to 24, carbon atoms.

[0040] Preferably, such aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, 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).

[0041] Aromatic ring may have any substituent, and from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary heteroatom.In addition, aromatic ring may have two or more aromatic rings connected by a linking group, and the linking group may contain the minimum necessary heteroatom.As heteroatom, for example, oxygen atom, nitrogen atom, sulfur atom, etc. can be mentioned.

[0042] An "aromatic ring" may contain at least one heteroatom selected from N, S and O on, within, or between the rings.

[0043] Examples of heteroatoms that may be included in the ring include, for example, a nitrogen atom contained in an amino group (e.g., a propargylamino group) or a cyano group; an oxygen atom contained in a formyl group, a hydroxy group, a carboxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group (e.g., a propargyloxy group), or an aryloxy group, which are oxygen-containing substituents; a nitrogen atom and an oxygen atom contained in a nitro group, which is an oxygen-containing substituent and a nitrogen-containing substituent. Examples of heteroatoms that may be included in the ring include, for example, an oxygen atom contained in furan or xanthene, a nitrogen atom contained in carbazole or pyrrole, and a sulfur atom contained in phenothiazine. Examples of heteroatoms that may be included in the linking group of two or more aromatic rings include a nitrogen atom, an oxygen atom, and a sulfur atom contained in -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-. In this specification, "the atoms constituting the aromatic ring" is synonymous with "the atoms contained in the ring". "The atoms bonded to the aromatic ring" refers to, for example, "the atoms directly bonded to the ring among the atoms or groups contained on the ring" and "the atoms directly bonded to the ring among the atoms contained between the rings". For example, the atoms constituting the benzene ring are carbon atoms. For example, the atoms constituting the pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of the hydroxyl group of phenol is not an atom constituting the aromatic ring. For example, the oxygen atom of the hydroxyl group of phenol is an atom bonded to the benzene ring and is an atom directly bonded to the benzene ring among the groups contained on the benzene ring.

[0044] <<<A-2: Exemplification of the Skeleton Constituting the Unit Structure (A)>>> The unit structure (A) has, for example, a skeleton having an aromatic ring.

[0045] Preferred skeletons having an aromatic ring include an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, and a phenol skeleton.

[0046] The unit structure (A) is, for example, a residue in which two hydrogen atoms have been removed from a skeleton having an aromatic ring. The skeleton having an aromatic ring is derived from, for example, 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).

[0047] 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 aryl group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxy 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. The alkyl group may be a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. The alkenyl group includes linear, branched or cyclic alkenyl groups having 2 to 10 carbon atoms. The alkynyl group includes linear, branched or cyclic alkynyl groups having 2 to 10 carbon atoms. The alkoxy group includes a group represented by -OR, where R is a saturated or unsaturated linear, branched or cyclic hydrocarbon group (-R a The alkoxy group may have 1 to 20 carbon atoms, for example. The aryl group includes an aryl group having 6 to 30 carbon atoms. The aryloxy group includes an aryloxy group having 6 to 30 carbon atoms. The amino group may be a group represented by -NH2, -NHR or -NR2, where R is the hydrocarbon group -R a In -NR2, the two R's may be the same or different. Examples of the hydroxyalkyl group include linear, branched or cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of the ester group include groups represented by -CO2R or -OCOR. Here, R represents the hydrocarbon group -R a . Examples of the amide group include groups represented by -NHCOR, -CONHR, -NRCOR or -CONR2. Here, R represents the hydrocarbon group -R a . When there are two Rs, the two Rs may be the same or different from each other. Examples of the sulfonyl-containing group include groups represented by -SO2R. Here, R represents the hydrocarbon group -R a or the hydroxy group -OH. Examples of the sulfide-containing group include groups represented by -SR. Here, R represents the hydrocarbon group -R a . Examples of the ether bond-containing group include residues of ether compounds containing an ether bond represented by R 11 -O-R 11 . Here, each R 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 including, for example, a methoxy group, an ethoxy group or a phenoxy group. 11

[0048] <<<<A-2-1: Aromatic amine skeleton>>>> The aromatic amine skeleton refers to a skeleton having an aromatic ring and a nitrogen atom bonded to the aromatic ring and not constituting the ring. Examples of the aromatic amine skeleton include skeletons represented by the following formulas (A-1a) to (A-1c). As described later, in the unit structure (A), the hydrogen atom of the NH group may be replaced by a substituent. Examples of the substituent include the substituents described in the above (I-3) "Aromatic ring", the substituents described in the above (A-2) "Examples of skeletons constituting the unit structure (A)", and the substituents (S) represented by the formulae (S1) to (S7) described later. [ka] (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.

[0049] Ar 11 and R 11 Examples of the aromatic ring in the aromatic ring residue include aromatic rings represented by the following formula (G1): These aromatic rings may have a substituent. [ka]

[0050] 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. [ka]

[0051] Examples of the skeleton represented by formula (A-1b) include the following skeletons. [ka]

[0052] Examples of the skeleton represented by formula (A-1c) include the following skeletons. [ka]

[0053] <<<<A-2-2: Nitrogen-containing aromatic heterocyclic skeleton>>>> The nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton having an aromatic heterocycle with a nitrogen atom in 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, a phenothiazine ring, and the like. These nitrogen-containing aromatic heterocycles may have a substituent. Examples of the nitrogen-containing aromatic heterocyclic skeleton include a skeleton represented by the following formula (A-2a), the following formula (A-2b-1), the following formula (A-2b-2), the following formula (A-2c-1), the following formula (A-2c-2), the following formula (A-2c-3), the following formula (A-2c-4), the following formula (A-2d), the following formula (A-2e), the following formula (A-3a), or the following formula (A-3b). As will be described later, in the unit structure (A), the hydrogen atom of the NH group may be replaced by a substituent. Examples of the substituent include the substituents described in the above (I-3) "aromatic ring", the substituents described in the above (A-2) "exemplification of the skeleton constituting the unit structure (A)", and the substituents (S) represented by the following formulas (S1) to (S7). [Chemical formula] [Chemical formula] (In the formula, Ar 21 each independently represents a residue of an aromatic ring. R 21 each independently represents a hydrogen atom or a residue of an aromatic ring. R 22 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a residue of an aromatic ring. Two adjacent R 22 may combine together to form an unsaturated aliphatic ring. One of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond constituting the 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 formulae (A-2b-2) and (A-2c-4), when L is a single bond, partial structures (In1) and (In2), and partial structures (Ca1) and (Ca2), respectively, are bonded by two nitrogen atoms being bonded 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 )

[0054] Ar 21 , R 21 , R 22 Examples of the aromatic ring in the aromatic ring residue of R include aromatic rings represented by the following formula (G2): These aromatic rings may have a substituent. [ka]

[0055] Two adjacent R 22 Examples of the unsaturated aliphatic ring formed by combining with each other include the following rings: These aliphatic rings may have a substituent. [ka]

[0056] Examples of the linking group for L include a (n1+n2)-valent saturated hydrocarbon group having 1 to 5 carbon atoms and a residue in which (n1+n2) hydrogen atoms have been removed from an aromatic ring.

[0057] <Formula (A-2d)> [ka] (In formula (A-2d), R 11 each independently represents a hydrogen atom or an aromatic group; Ar is an aromatic ring moiety, each independently being a benzene ring, a fused ring composed of 2 to 3 benzene rings, or a structure represented by the following formula (Ar01): X 0 is a single bond, -O-, -S-, -NR 12 -or-CR 13 R 14 - represents 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.

[0058] In the unit structure (A), R in formula (A-2d) 11 may be a substituent. R 11 When R is a substituent or an aromatic group, 11 For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) represents 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, However, with regard to (ii) and (iii) above, they may be further substituted with an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, an aryl group or a halo group, and with regard to (iii) above, the hydrocarbon chain portion may be further interrupted by an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent or an arylene group.

[0059] An example of the skeleton represented by formula (A-2d) is the skeleton represented by the following formula (A-2d-1). [ka] (R in formula (A-2d-1) 11 , Ar, and X 0 respectively represent R in formula (A-2d). 11 , Ar, and X 0 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.

[0060] In the formula (A-2d) and the formula (A-2d-1), Ar is, for example, a benzene ring or a naphthalene ring. Ar in the formula (A-2d) and the formula (A-2d-1) may be a structure represented by the following formula (Ar01). [ka] (R in formula (Ar01) 11a R in formula (A-2d-1) 11 is synonymous with R 21a R in formula (A-2d-1) 21 is synonymous with Ar a has the same meaning as Ar in formula (A-2d-1), and X 0a is X in formula (A-2d-1). 0 is synonymous with. In the two carbon atoms a and b, b and c, or c and d in the formula (Ar01), X in the formula (A-2d) or the formula (A-2d-1) 0 )

[0061] where X 0 The monocyclic moiety containing the following formula (AP011) in formula (A-2d) represents a monocyclic ring represented by the following formula (AP011). [ka]

[0062] As the skeleton represented by formula (A-2d), a skeleton represented by the above formula (A-2d-1), a skeleton represented by the following formula (A-2d-2), or a skeleton represented by the following formula (A-2d-3) is preferable. [ka] (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 is synonymous with. L represents a single bond or a divalent linking group, and examples of the divalent linking group include -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, and -NR 101 -,―(CR 102 R 103 )m 1 -, -(Ar 101 )m 2 -, -CH2-(Ar 101 )m 2 R represents -CH2- 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 from 1 to 10. And, Ar 101 each independently represents an arylene group having 6 to 30 carbon atoms; 2 represents the number of aromatic rings bonded to each other by single bonds, which is 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. R 22 each independently represents an optionally substituted arylene group having 6 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms.

[0063] <Formula (A-2e)> [ka] 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; R 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, Ar 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).

[0064] In the unit structure (A), R in formula (A-2e) 11 and R 21 may be a substituent. R 11 and R 21 When R is a substituent or a residue of an aromatic group, 11 and R 21 For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) represents 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, However, with regard to (ii) and (iii) above, they may be further substituted with an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, an aryl group or a halo group, and with regard to (iii) above, the hydrocarbon chain portion may be further interrupted by an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent or an arylene group.

[0065] 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 Or Ar 2 , i.e., in the azaaryl condensed ring [ka] and [ka] However, it is preferably bonded to a carbon atom constituting the pyrrole ring portion in the azaaryl condensed ring.

[0066] Preferred linking groups (L) include -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, -(CR 102 R 103 )m 1 -,―(Ar 101 )m 2 -, -CH2-(Ar 101 )m 2 -CH-, and -(cyclo-R)-. 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 from 1 to 10. And, Ar 101 each represents an arylene group having 6 to 30 carbon atoms; 2 represents the number of aromatic rings bonded to each other by single bonds, which is 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.

[0067] <Formula (A-3a) and Formula (A-3b)> [ka] (In the formula, Ar 31 and Ar 32each independently represents the residue of an aromatic ring, or together with the carbon atom to which it is attached represents the residue of an aromatic ring; X represents -O, -S-, -NH-, -CH2-, -CH2-CH2-, or -CH=CH-.

[0068] Ar 31 and Ar 32 Examples of the aromatic ring in the aromatic ring residue include the aromatic ring represented by the above formula (G1). Ar 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.

[0069] 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 atom of the NH group may be replaced with a substituent. The same applies to the following skeletons. [ka]

[0070] Examples of the skeleton represented by formula (A-2b-1) include the following skeletons. [ka]

[0071] Examples of the skeleton represented by formula (A-2b-2) include the following skeletons. [ka]

[0072] Examples of the skeleton represented by formula (A-2c-1) include the following skeletons. [ka]

[0073] Examples of the skeleton represented by formula (A-2c-2) or formula (A-2c-3) include the following skeletons. [ka]

[0074] Examples of the skeleton represented by formula (A-2c-4) include the following skeletons. [ka]

[0075] Examples of the skeleton represented by formula (A-2d) include the following skeletons. [ka] [ka] [ka] [ka] [ka] [ka]

[0076] 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. [ka] [ka] [ka]

Chem.

[0077] Examples of the skeleton represented by formula (A-3a) include the following skeletons.

Chem.

[0078] Examples of the skeleton represented by formula (A-3b) include the following skeletons.

Chem.

[0079] Examples of other skeletons of the nitrogen-containing aromatic heterocyclic skeleton include the following skeletons.

Chem.

Chem.

[0080] <<<<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 plural. In the case of plural, it may be 2 to 10 or 2 to 8. In the case of plural, the hydroxy groups may be bonded to the same aromatic ring (for example, a benzene ring) or to different aromatic rings. As described later, 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 the above (I-3) "Aromatic ring", the substituents described in the above (A-2) "Examples of skeletons constituting the unit structure (A)", and the substituents (S) represented by the formulae (S1) to (S7) described later.

[0081] 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 hydroxyl group may be replaced with a substituent. The same applies to the following skeletons. [ka] (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, with the proviso 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.)

[0082] Examples of the phenol skeleton include skeletons represented by the following formula (A-5a), (A-5b), (A-5c), or (A-5d). [ka] (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 represents an alkylene group which may be substituted with -O-, -CO-, -S-, -SO2- or a halogen atom. When k1 is 1, X 21 represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group which may be substituted with a halogen atom. When k2 is 1, X 22represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group which may be substituted with a halogen atom. When k1 is 2, X 21 represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. When k2 is 2, X 22 represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. Y 1 represents a trivalent saturated hydrocarbon group. Y 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 total of m3 to m5 is 1 or more. m6 to m8 each independently represent an integer of 0 to 3, provided that the total 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.

[0083] Ar 41 Examples of the aromatic ring in the aromatic ring residue include aromatic rings represented by the following formula (G3): These aromatic rings may have a substituent. [ka]

[0084] X 1 , and X 2 The number of carbon atoms of 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.

[0085] Y 1 , and Y 2The number of carbon atoms in the saturated hydrocarbon group 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.

[0086] 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). [ka] [ka] [ka] (In the formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (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 a bridge structure between the aromatic rings as an ether bond, and when p is 0, there is no ether bond that forms a bridge structure between the aromatic rings. L represents a single bond or a divalent linking group.

[0087] Ar 51 Examples of the aromatic ring in include the aromatic ring represented by the above formula (G1), and a benzene ring and a naphthalene ring are preferred. Examples of L include divalent groups obtained by removing two hydrogen atoms from the following structures: [ka]

[0088] For example, each n11 independently represents 1 or 2.

[0089] Examples of the phenol skeleton include skeletons represented by the following formula (A-7a), (A-7b), or (A-7c). [ka] (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar 61 each independently represents a residue of an aromatic ring; each n21 independently represents an integer of 1 to 4.

[0090] Ar 61 Examples of the aromatic ring in include the aromatic ring represented by the above formula (G1), and a benzene ring and a naphthalene ring are preferred. For example, each n21 independently represents 1 or 2.

[0091] 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). [ka] In formulae (A-8a-1), (A-8b), (A-8c), (A-8e), (A-8f), (A-8g-1), and (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 greater. 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 greater. In formula (A-8b), X 1 represents -O- or -NH-. In formula (A-8d), X 2 represents -O-, -S-, or -CH2-. In formula (A-8e), X 3represents -S-, -CH2-, or -NH-. In formula (A-8f), X 4 represents -CO- or -O-; X 5 represents -CH2- or -O-.

[0092] For example, each n31 independently represents 1 or 2. For example, n32 and n33 each independently represent 0, 1 or 2.

[0093] 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 hydroxyl groups may be replaced with a substituent. The same applies to the following skeletons. [ka] [ka]

[0094] Examples of the skeleton represented by formula (A-5a) include the following skeletons. [ka]

[0095] Examples of the skeleton represented by formula (A-5b) include the following skeletons. [ka]

[0096] Examples of the skeleton represented by formula (A-5c) include the following skeletons. [ka]

[0097] Examples of the skeleton represented by formula (A-5d) include the following skeleton. [ka]

[0098] Examples of the skeleton represented by formula (A-6a) include the following skeletons. [ka]

[0099] Examples of the skeleton represented by formula (A-6b-1) or formula (A-6b-2) include the following skeletons. [ka]

[0100] Examples of the skeleton represented by formula (A-6c) include the following skeletons. [ka]

[0101] Examples of the skeleton represented by formula (A-6d) include the following skeleton. [ka] [ka]

[0102] Examples of the skeleton represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following skeletons. [ka]

[0103] Examples of the skeleton represented by formula (A-8a-1) or formula (A-8a-2) include the following skeletons. [ka]

[0104] Examples of the skeleton represented by formula (A-8b) include the following skeleton. [ka]

[0105] Examples of the skeleton represented by formula (A-8c) include the following skeletons. [ka]

[0106] Examples of the skeleton represented by formula (A-8d) include the following skeleton. [ka]

[0107] Examples of the skeleton represented by formula (A-8e) include the following skeleton. [ka]

[0108] Examples of the skeleton represented by formula (A-8f) include the following skeletons. [ka]

[0109] Examples of the skeleton represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons. [ka]

[0110] Examples of other skeletons of the phenol skeleton include the following skeletons. [ka]

[0111] In addition, H of NH in the skeleton having an aromatic ring, H of a hydroxy group bonded to the aromatic ring in the skeleton having an aromatic ring, and a hydrogen atom bonded to the aromatic ring in the skeleton having an aromatic ring may be replaced with a substituent. Examples of the substituent include the substituents (S) represented by the following formulae (S1) to (S7).

[0112] [ka] (In formulas (S1) to (S7), R sa represents a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. R sb each independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. R sc each independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. R sd alkynyl each independently represents an alkynyl group having 2 to 4 carbon atoms. Ar sa each independently represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar sb each independently represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. X 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 sb together with the carbon atom bonded to the hydroxy group, constitutes a carbonyl group. n represents an integer of 0 to 5. * represents a bond.)

[0113] <R sa > Rsa In the above formula, examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms 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 be conjugated or non-conjugated.

[0114] <R sb , and R sc > R sb , and R sc Examples of the divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms in the formula 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 be conjugated or non-conjugated. R sb , and R sc Examples of the group include the following groups. [ka] (* represents a bond.)

[0115] <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).

[0116] <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.

[0117] <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.

[0118] <X sa and X sb > X sa and X sb Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include alkyl groups 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.

[0119] Examples of the substituent represented by formula (S1) include the following groups. [ka] (* represents a bond.)

[0120] Examples of the substituent represented by formula (S2) include the following groups. [ka] (* represents a bond.)

[0121] Examples of the substituent represented by formula (S3) include the following groups. [ka] (* represents a bond.)

[0122] Examples of the substituent represented by formula (S4) include the following groups. [ka] (* represents a bond.)

[0123] Examples of the substituent represented by formula (S5) include the following groups. [ka] (* represents a bond.)

[0124] Examples of the substituent represented by formula (S6) include the following groups. [ka] (* represents a bond.)

[0125] Examples of the substituent represented by formula (S7) include the following groups. [ka] (* represents a bond.)

[0126] Examples of other substituents include the following groups: [ka] (* represents a bond.)

[0127] 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 may extend from any possible carbon atom, and the positions are not limited thereto.

[0128] (Example of a unit structure composed of an aromatic amine skeleton) -NH- can also have a structure in which the hydrogen atom on N is replaced.

[0129] [ka] [ka] [ka]

[0130] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons) [ka] [ka]

[0131] (Example of a unit structure composed of a phenol skeleton) [ka] [ka] [Chemical formula] [Chemical formula] [Chemical formula]

[0132] [<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 unit structures including a linking carbon atom (see the above (I-1)) that binds to the aromatic ring in the unit structure (A), and includes, for example, structures represented by the following formulas (B1), (B2), or (B3) described later. The unit structure (B) can link two unit structures (A) by covalent bonding with the unit structure (A).

[0133] [<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). [Chemical formula] 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 fewer carbon atoms which may have a substituent. R and R' may together with the carbon atom to which they are attached form a structure having a ring structure. * represents a bond.

[0134] 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 the H of a hydroxy group is substituted with the above-mentioned substituent (S), and a halo group.

[0135] Furthermore, the two bonds in the formula (B1) can be covalently bonded to the aromatic rings in the two unit structures (A), respectively.

[0136] In the definitions of R and R' in formula (B1), for the terms "aromatic ring" and "heterocycle", see (I-3) and (I-4) above.

[0137] 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, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl ethyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl cyclopropyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-i-propylcyclopropyl, 2-i-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,Examples of the cyclopropyl group include 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0138] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0139] Examples of the structure having a ring structure formed by R and R' together with the carbon atom to which they are bonded include structures represented by the following formulas. [ka] (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).)

[0140] The aromatic ring of Ar includes, for example, an aromatic ring represented by the formula (G1).

[0141] The unit structure (B) containing the structure represented by formula (B1) is derived from, for example, an aldehyde compound or a ketone compound. An example of the aldehyde compound is a compound represented by the following formula (B-1a). An example of the ketone compound is a compound represented by the following formula (B-1b). [ka] 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.

[0142] For example, when obtaining the resin (G), the carbonyl groups in the formula (B-1a) and the formula (B-1b) are converted to *-C-* in the formula (B1).

[0143] Some specific examples of the unit structure (B) containing the structure represented by the formula (B1) are as follows. * basically indicates the bonding site with the unit structure (A). Needless to say, a structure containing a part of the exemplified structure as a part of the whole may also be used.

[0144]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0145] <<<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).

[0146]

Chemical formula

[0147] 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 the H of a hydroxy group is substituted with the above-mentioned substituent (S), and a halo group.

[0148] 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, etc.) 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.

[0149] 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-position carbon atom (such as the benzylic carbon atom) of an alkylaryl group, or a compound having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0150] An example of the compound having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom is a compound represented by the following formula (B-2a). Examples of compounds having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-position carbon atom (such as the benzylic carbon atom) of an alkylaryl group include compounds represented by the following formula (B-2b). Examples of the compound having two carbon-carbon double bonds include compounds represented by the following formula (B-2c) or (B-2d). [ka] (In formula (B-2a), formula (B-2b), and formula (B-2b), J 1 , J2 , and Z 0 is J in formula (B2) 1 , J 2 , and Z 0 are synonymous, respectively. 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. In formula (B-2b), Y a , and Y b each independently represents 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. In formula (B-2d), n represents an integer of 0 to 4.

[0151] For example, when preparing the resin (G), X in the formula (B-2a) a -J 1 In formula (B2), *-J 1 It is converted into J 2 -X b In formula (B2), J 2 Converted to -*. For example, when preparing resin (G), Y a -J 1 In formula (B2), *-J 1 It is converted into J 2 -Y b In formula (B2), J 2 Converted to -*.

[0152] An example of formula (B-2a) is the compound below. [ka]

[0153] An example of formula (B-2b) is the compound below. [ka]

[0154] An example of formula (B-2c) is the following compound.

Chemical formula

[0155] Some specific examples of the unit structure containing the structure represented by formula (B2) are as follows. * indicates the bonding site with the unit structure (A). Needless to say, the unit structure may also be one that includes the exemplified structure as a part of the whole.

[0156]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0157] <<<B-4: Formula (B3)>>>

Chemical formula

[0158] 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-Huckel monocycle"); at least one of the monocycles constituting the two, three, and four rings 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).

[0159] The monocyclic ring, or the 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 number of carbon atoms in the pentacyclic or higher fused ring is preferably 40 or less. 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.

[0160] X and Y may be the same or different, -CR 31 R 32 - group, 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.

[0161] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1.

[0162] In formula (B3), [ka] And, in formula (B3), [ka] 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).

[0163] For example, in formula (B3), [ka] is bonded to any carbon atom (referred to as "carbon atom 1") constituting the non-Hückel monocyclic ring of Z (when x=1) or extends from carbon atom 1 (when x=0),

[0164] In formula (B3), [ka] 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 when they are different, they may belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0165] Furthermore, in formula (B3), optionally, linking carbon atoms other than carbon atom 1 and carbon atom 2 may be included. When Z is a tricyclic or higher fused ring, the permutation 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 relationship between non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary. Specific examples of the organic group containing the structure represented by formula (B3) are as follows. The bonding site with the unit structure A is not particularly limited. Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0166] Although examples including more than two bonds (*) are included, these excess bonds can be used for bonding to aromatic rings in other polymer chains, crosslinking, etc., or can serve as bonds to hydrogen bonds.

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] Hereinafter, in formula (B3), [ka] And, in formula (B3), [ka] Hereinafter, only one of the above will be described, in which x=1, y=1 is bonded to any of the carbon atoms constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") or extends from the carbon atom Z (x=0, y=0). As a more specific structure of formula (B3) in this case, for example, in the following formula (C31), among p, k1, and k2 which can be bonds, p and k1, or p and k2, can form a unit structure (B) represented by formula (B3). The remaining bonds are bonded to hydrogen atoms.

[0174] [ka] In addition, in the following formula (C32), among p, k1, k2, and m which can be bonds, p and k1, p and k2, or p and m can form a unit structure (B) represented by formula (B3). The remaining bonds are bonded to hydrogen atoms.

[0175] [ka] Some specific examples of formula (B3) corresponding to formula (C31) or formula (C32) are as follows: * indicates the bonding site with unit structure (A).

[0176] In formula (B3), the aromatic rings in these structures have bonds extending therefrom to other unit structures (e.g., unit structure (A)), but in the specific examples below, such bonds are omitted. Needless to say, the unit structures may include the exemplified structures as part of the whole. [ka] [ka] [ka] In the above specific examples, when there is no bond from the aromatic ring, it can be a specific example of a polymer end.

[0177] The novolak resin having the structure represented by formula (AB) can be prepared by a known method. For example, it can be prepared by condensing a ring-containing compound represented by HAH with an oxygen-containing compound represented by OHC-B, O=CB, RO-B-OR, RO-CH2-B-CH2-OR, etc. In the formula, A and B are as defined above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0178] The ring-containing compound and the oxygen-containing compound may each be used alone or in combination of two or more. In this condensation reaction, the oxygen-containing compound can be used in a ratio of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the ring-containing compound.

[0179] Examples of the catalyst used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid. The amount of the catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, per 100 parts by mass of the ring-containing compound (the total amount when multiple types are used).

[0180] The condensation reaction can be carried out without a solvent, but is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction. Examples of the solvent include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, tetrahydropyran, dioxane, 1,2-dichloromethane, 1,2-dichloroethane, toluene, N-methylpyrrolidone, and dimethylformamide. The condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0181] The weight average molecular weight of the novolac resin according to one embodiment of the present invention is usually 500 to 100,000, and preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0182] The content of the resin (G) in the composition for forming a protective film is, for example, preferably from 25 to 100 mass %, more preferably from 50 to 100 mass %, and even more preferably from 70 to 100 mass %, based on the film-constituting components. Here, the film-constituting components refer to the components remaining after removing the solvent component from the protective film-forming composition.

[0183] The molar ratio ((A):(B)) of the unit structure (A) to the unit structure (B) in the resin (G) is, for example, preferably 30:70 to 70:30, more preferably 30:70 to 50:50, further preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. The molar ratio of unit structure (A) to unit structure (B) in resin (G) can also be expressed as the molar ratio of compound (A) serving as a raw material for unit structure (A) to compound (B) serving as a raw material for unit structure (B). The molar ratio ((A):(B)) of the compound (A) to the compound (B) is, for example, preferably 30:70 to 70:30, more preferably 30:70 to 50:50, further preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. Here, the compound (A) may be one type or two or more types. Similarly, the compound (B) may be one type or two or more types.

[0184] The content ratio of the unit structure (AI) in the unit structure (A) (molar ratio ((AI) / (A))) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and may be 100 mol%. The content (molar ratio) of the unit structure (AI) in the unit structure (A) can also be expressed as the molar ratio of the compound (AI) that is the raw material of the unit structure (AI) in the compound (A). The molar ratio of compound (AI) in compound (A) ((AI) / (A)) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and may be 100 mol%.

[0185] The content ratio of unit structure (BI) in unit structure (B) (molar ratio ((BI) / (B))) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and may be 100 mol%. The content (molar ratio) of unit structure (BI) in unit structure (B) can also be expressed as the molar ratio of compound (BI) which is a raw material of unit structure (BI) in compound (B). The molar ratio of compound (BI) in compound (B) ((BI) / (B)) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and may be 100 mol%.

[0186] <Solvent> Examples of the solvent contained in the protective film forming composition of the present invention include water and organic solvents. Examples of the organic solvent include 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 (PGME), propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol diacetate, 1,4 -butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0187] In addition, it is preferable to use a solvent having an evaporation rate of 0.05 or less (sometimes referred to as a "first solvent"). Here, the evaporation rate used in the present invention is the evaporation rate obtained by ASTM D 3539. However, the evaporation rate value used in the present invention is a relative value to the evaporation rate of n-butyl acetate. That is, the evaporation rate value used in the present invention is the value obtained by dividing the evaporation rate of the solvent by the evaporation rate of n-butyl acetate.

[0188] The evaporation rate of the first solvent is 0.05 or less, preferably 0.04 or less, and more preferably 0.03 or less.

[0189] From the viewpoint of forming a protective film with good film quality on the edge (surface edge and bevel) of a wafer for semiconductor manufacturing by a simple method of coating, the first solvent is preferably used in combination with the second solvent, i.e., the solvent preferably contains the first solvent and the second solvent. For example, it was found that when a solvent with a high evaporation rate (easy to evaporate) is used alone as the solvent for the protective film-forming composition, the coverage of the surface edge is good, but the film shape of the bevel portion is poor (for example, partial swelling or depression occurs). On the other hand, it was found that when a solvent with a low evaporation rate (difficult to evaporate) is used alone, the film shape of the bevel portion is good, but the coverage of the surface edge is poor (film thickness becomes thin). Furthermore, it was difficult to achieve both by using a solvent with an intermediate evaporation rate alone. That is, it was found that it is difficult to improve both the coverage of the surface edge and the film shape of the bevel portion with only one type of solvent. Therefore, by using two or more solvents with different evaporation rates in combination, a protective film with good film quality can be formed by a simple method of coating on the edge (surface edge and bevel) of a wafer for semiconductor manufacturing.

[0190] The first solvent and the second solvent are, for example, organic solvents. The evaporation rate of the second solvent is, for example, 0.10 or more, preferably 0.10 to 0.80, more preferably 0.20 to 0.60, and particularly preferably 0.30 to 0.50.

[0191] The difference (V2-V1) between the evaporation rate (V2) of the second solvent and the evaporation rate (V1) of the first solvent is not particularly limited, but from the viewpoint of forming a protective film with good film condition, it is preferably 0.10 or more, more preferably 0.15 or more, and particularly preferably 0.20 or more. Moreover, the difference (V1-V2) is preferably 0.70 or less, more preferably 0.60 or less, and particularly preferably 0.50 or less.

[0192] The mass ratio (S1:S2) of the first solvent (S1) to the second solvent (S2) is not particularly limited, but from the viewpoint of forming a protective film with good film quality, it is preferably 50:50 to 95:5, more preferably 60:40 to 93:7, and particularly preferably 70:30 to 90:10.

[0193] Here, an example of the evaporation rate (the evaporation rate of n-butyl acetate is taken as 1) is shown below.

[0194] [Table 1]

[0195] The solvent may include an organic solvent other than the first solvent and the second solvent.

[0196] The total proportion of the first solvent and the second solvent in the solvent is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

[0197] The content of the solvent in the composition for forming a protective film is not particularly limited, but is preferably 70% by mass to 99% by mass, more preferably 75% by mass to 98% by mass, and particularly preferably 80% by mass to 95% by mass.

[0198] The total content of the first solvent and the second solvent in the composition for forming a protective film is not particularly limited, but is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 98% by mass, and particularly preferably 75% by mass to 95% by mass.

[0199] <Acid, etc.> The composition for forming a protective film may contain an acid and / or a salt thereof and / or an acid generator.

[0200] Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid.

[0201] As the salt, a salt of the above-mentioned acid can also be used. As the salt, although it is not limited, ammonia derivative salts such as trimethylamine salts and triethylamine salts, pyridine derivative salts, morpholine derivative salts, etc. can be suitably used.

[0202] The acid and / or its salt may be used alone or in combination of two or more. The amount of the acid and / or its salt to be added is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the membrane constituent components.

[0203] The acid generator includes a thermal acid generator and a photoacid generator.

[0204] Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), as well as SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0205] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the protective film to be adjusted. This is one way to match the acidity of the protective film to that of the resist. In addition, adjusting the acidity of the protective film allows the pattern shape of the resist to be adjusted.

[0206] Examples of the photoacid generator contained in the composition for forming a protective film include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0207] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal 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 nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0208] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0209] 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.

[0210] The acid generators may be used alone or in combination of two or more.

[0211] When an acid generator is used, the proportion thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, per 100 parts by mass of the film-constituting components of the composition for forming a protective film.

[0212] <Other ingredients> In addition to the above, the composition for forming a protective film may contain a crosslinking agent, a surfactant, a light absorbing agent, a rheology adjusting agent, an adhesive auxiliary, and the like, if necessary.

[0213] Representative examples of crosslinking agents include aminoplast crosslinking agents and phenoplast crosslinking agents.

[0214] As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in the molecule can be preferably used.

[0215] Aminoplast crosslinkers include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, and polymers thereof.Preferably, the crosslinker has at least two crosslink-forming substituents, and is a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea.Condensates of these compounds can also be used.

[0216] Preferably, it is at least one selected from the group consisting of tetramethoxymethylglycoluril and hexamethoxymethylmelamine.

[0217] Some specific examples are as follows:

[0218] [ka]

[0219] Phenoplast crosslinkers include highly alkylated, alkoxylated, or alkoxyalkylated aromatics, their polymers, etc. Preferably, the crosslinker has at least two crosslink-forming substituents in one molecule, and is a compound such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene, etc. Condensates of these compounds can also be used.

[0220] In addition to the above, other examples of such compounds include compounds having a partial structure of the following formula (4) and polymers or oligomers having a repeating unit of the following formula (5).

[0221] [ka] Above R 11 , R 12 , R 13 , and R 14 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the above-mentioned examples of the alkyl group can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. The number of repeating unit structures of the oligomers and polymers that can be used is in the range of 2 to 100 or 2 to 50.

[0222] Some specific examples are as follows:

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] The crosslinking agents such as aminoplast crosslinking agents and phenoplast crosslinking agents may be used alone or in combination of two or more. The aminoplast crosslinking agent may be produced by a method known per se or a method equivalent thereto, or a commercially available product may be used.

[0228] In addition, the amount of crosslinking agent such as aminoplast crosslinking agent or phenoplast crosslinking agent used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more relative to the film constituent components of the composition for forming a protective film, and is 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less.

[0229] The composition for forming a protective film may contain a surfactant in order to prevent pinholes, striations, etc., and to further improve the coatability against surface unevenness.

[0230] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers, such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Fluorine-based surfactants such as EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product names), Megafac F171, F173, R-30, R-40 (manufactured by Dainippon Ink Co., Ltd., product names), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited, product names), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product names), etc. Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

[0231] 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 film-constituting components of the composition for forming a protective film. These surfactants may be added alone or in combination of two or more kinds.

[0232] Examples of the light absorbing agent include commercially available light absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthesis Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CID isperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbing agent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbing agent is usually blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the film constituent components of the composition for forming a protective film.

[0233] The rheology control agent is added mainly to improve the fluidity of the protective film forming composition, and to improve the thickness uniformity of the protective film, especially in the baking process.Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl adipate, maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate, and stearic acid derivatives such as n-butyl stearate and glyceryl stearate.These rheology control agents are usually blended in a ratio of less than 30% by mass with respect to the film constituents of the protective film forming composition.

[0234] The adhesion promoter is added mainly for the purpose of improving the adhesion of the substrate or the protective film forming composition, and in particular for the purpose of preventing the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesive auxiliary include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive auxiliary agents are usually blended in a proportion of less than 5% by mass, and preferably less than 2% by mass, based on the film constituent components of the protective film-forming composition.

[0235] The method for preparing the composition for forming a protective film is not particularly limited. That is, the resin (G), the solvent, and other components may be mixed in any ratio and in any order to prepare a homogeneous solution. The composition for forming a protective film in the form of a solution thus prepared is preferably used after filtering using a filter having a pore size of about 0.2 μm.

[0236] As described later, in order to prepare a protective film having a thickness of about 300 nm by a spin coating method, the composition for forming the protective film preferably has a viscosity of about 100 cps or less at 25° C., more preferably 50 cps or less, and particularly preferably 10 cps or less. In the present invention, the viscosity is a value measured at 25° C. using an E-type viscometer.

[0237] (protective film) The protective film of the present invention is a cured product of a coating film made of the protective film-forming composition of the present invention. An example of a method for forming the protective film is step (X) in the method for producing a semiconductor device, which will be described later. The protective film is, for example, a protective film for preventing metal contamination of the edge of the wafer.

[0238] In this specification, the edge of the wafer refers to a region of the outer periphery of the wafer that cannot be used and is not suitable for producing semiconductor elements. The edge of the wafer includes not only the flat edge at the outer periphery of the wafer, but also the chamfered peripheral end surface (bevel portion, apex portion, etc.) of the edge of the wafer at the outer periphery. Moreover, the edge of the wafer includes not only the edge of the front surface (surface) but also the edge of the back surface (reverse surface). The edge of the wafer refers to, for example, a flat edge on the outer periphery of the front surface, a bevel portion or apex portion on the peripheral edge face, and a flat edge on the outer periphery of the back surface.

[0239] The edge of the wafer will be described with reference to FIG. 1A or FIG. 1B. 1A and 1B are enlarged cross-sectional views showing an edge of a wafer (substrate). More specifically, FIG. 1A is a cross-sectional view of a so-called straight type substrate, and FIG. 1B is a cross-sectional view of a so-called round type substrate. In the wafer W (an example of a substrate) of FIG. 1A, the edge of the wafer is an unusable portion of the outer periphery of the wafer, a portion that is not suitable for making a semiconductor element, and the edge of the wafer includes, for example, a flat edge Ed1 at the outer periphery of the front surface. The edge of the wafer also includes, for example, a peripheral edge surface V that is chamfered from the edge of the outer periphery of the wafer. The peripheral edge surface V is composed of an upper inclined portion (upper bevel portion) S, a side portion (apex) T, and a lower inclined portion (lower bevel portion) U. The above (upper bevel portion) is also referred to as the bevel portion on the front side (front surface), and the above (lower bevel portion) is also referred to as the bevel portion on the back side (back surface). The edge of the wafer also includes, for example, a flat edge Ed2 at the outer periphery of the back surface. 1B, the edge of the wafer W includes Ed1, Ed2, and a peripheral edge surface V having a curved cross section that constitutes the outermost peripheral surface of the wafer W. In addition, in FIG. 1B, the peripheral edge surface V is also referred to as a bevel portion.

[0240] The lower limit of the thickness of the protective film is, for example, 1 nm, 3 nm, 5 nm, 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1,000 nm, 1,500 nm, or 1,700 nm. The upper limit of the thickness of the protective film is, for example, 10,000 nm, 9,000 nm, 8,000 nm, 7,000 nm, 6,000 nm, 5,000 nm, 4,000 nm, 3,800 nm, 3,700 nm, 3,600 nm, 3,500 nm, 3,300 nm, 3,000 nm, 2,500 nm, 2,000 nm, 1,500 nm, 1,000 nm, 800 nm, 500 nm, or 300 nm.

[0241] The properties of the protective film that covers the edges of substrates (wafers) used in semiconductor manufacturing (e.g., the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and the flat edge of the back surface) desirably satisfy, in addition to the function of preventing metal contamination, dry etching resistance, phosphoric acid resistance, tetramethylammonium hydroxide (TMAH) resistance, HF removability, scratch resistance, good embedding ability for stepped substrates, low amount of sublimation, affinity for hydrophobic substrates, no crater foreign matter remaining on the wafer side (bevel portion or apex portion), good edge shape, and the function of suppressing inner humps (the phenomenon in which a film-forming composition remains in a lump shape directly below the nozzle injection hole).

[0242] (Method of manufacturing a semiconductor device) The method for manufacturing a semiconductor device according to the present invention includes the steps of: (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; (C) etching the semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: The method includes the step (X) of forming a protective film on an edge of a wafer for semiconductor manufacturing (for example, a flat edge of the front surface, a peripheral edge surface (bevel portion, apex portion, etc.), and optionally a back surface edge) using the protective film-forming composition of the present invention; A method for manufacturing a semiconductor device.

[0243] The following explains each in order. <Process (A)> In step (A), a resist film is formed on a semiconductor substrate. The semiconductor substrate is a wafer used for manufacturing semiconductor devices and the like, and in addition to commonly used silicon wafers and germanium wafers, for example, compound semiconductor wafers formed by combining two or more elements such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride can be used. These are usually disk-shaped and have sizes of, for example, 4, 6, 8, or 12 inches. Commercially available products may be used.

[0244] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin-coating (spin-on glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0245] On such a semiconductor substrate, a resist underlayer film, a resist film, etc., of a predetermined thickness are formed by an appropriate coating method such as spray, spinner, coater, etc. In general, in the case of a spin coating method, the resist underlayer film forming composition, the resist film forming composition, etc. are each supplied from above the center of a rotating disk-shaped substrate through a nozzle, etc. Usually, these films are baked using a heating means such as a hot plate.

[0246] The photoresist used to form the resist film is not particularly limited as long as it is sensitive to the light used for exposure. In this specification, electron beam resist is also included in the photoresist. Both negative photoresists and positive photoresists can be used. There are positive photoresists made of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements. Examples of the photoresist include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, examples of the photoresist include fluorine atom-containing polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000). Negative photoresists are preferred.

[0247] The resist film forming composition used for forming the resist film can contain one or more metals. The form of the metal can be a simple metal, a metal salt, a metal complex, or other metal-containing compounds. The metal species is not particularly limited, and examples thereof include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium.

[0248] The resist film forming composition used to form the resist film may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions comprising metal oxo-hydroxo networks having organic ligands via metal carbon bonds and / or metal carboxylate bonds, as described in JP 2019-113855 A. An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Peroxo-based metal oxo-hydroxo compounds are described in detail in, for example, the patent document described in paragraph

[0011] of Publication 2019-532489. Such patent documents include, for example, U.S. Pat. No. 9,176,377 B2, U.S. Pat. Appl. Pub. No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Pat. Appl. Pub. No. 2016 / 0116839 A1, and U.S. Pat. Appl. Pub. No. 15 / 291738.

[0249] The bake conditions for the resist film are appropriately selected from a bake temperature of 70° C. to 400° C. and a bake time of 0.3 to 60 minutes, preferably a bake temperature of 80° C. to 350° C. and a bake time of 0.5 to 30 minutes, and more preferably a bake temperature of 90° C. to 300° C. and a bake time of 0.8 to 10 minutes.

[0250] The lower limit of the average thickness of the resist film is preferably 1 nm, more preferably 3 nm, 5 nm, or 10 nm.The upper limit of the average thickness of the resist film is 5,000 nm, 3,000 nm, or 2,000 nm, preferably 1,000 nm, more preferably 200 nm, and more preferably 50 nm.

[0251] <Process (X) of forming protective film> Step (X) of forming a protective film using the protective film-forming composition of the present invention is carried out at any time on the edge of a wafer for semiconductor manufacturing (e.g., the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the back surface edge). In step (X), the protective film-forming composition is preferably applied. Step (X) may be carried out before step (A), between steps (A) and (B), or after step (B) or step (C).

[0252] As described above, in this specification, the surface of the substrate on which the device portion such as a resist film is provided is referred to as the front surface, and the opposite surface is referred to as the back surface. The edge of the front surface refers to a region usually having a width of 1 to 10 mm from the edge of the device portion provided on the substrate to the bevel portion (or apex portion), the bevel portion (or apex portion) refers to a curved region (the side surface of the wafer, corresponding to the above-mentioned "peripheral edge surface") connecting the flat edge of the front surface and the flat edge of the back surface, and the edge of the back surface refers to a region corresponding to the front surface edge of the back surface of the substrate.

[0253] First, the composition for forming a protective film is applied to the semiconductor substrate. The method for applying the composition for forming a protective film is not particularly limited, but for example, known means such as a spin coating method (spin coating method) or a spray method can be adopted. For example, when the spin coating method is adopted, the composition for forming a protective film is supplied through a nozzle from above or near the front end of the rotating disk-shaped substrate while rotating the semiconductor substrate at a predetermined rotation speed. Preferably, the composition is also supplied through a nozzle from the vicinity of the peripheral end surface and / or back end of the substrate.

[0254] The spin-coating conditions can be appropriately selected and are not limited in any way. Typical conditions are as follows: Viscosity of protective film forming composition: Approximately 100 cps or less Wafer rotation speed: ·When supplying the composition for forming a protective film: 50~500 rpm When shaking off the dry air: 700 to 2,000 rpm Protective film thickness: 300nm

[0255] After coating, heating may be performed as necessary. For example, a protective film can be obtained by heating. The heating temperature is, for example, 80°C to 800°C, and preferably 150°C to 500°C. The heating time is, for example, 0.3 to 60 minutes, and preferably 0.5 to 2 minutes. The heating is performed using, for example, a hot plate, a proximity bake furnace, or the like.

[0256] For example, step (X) is performed before step (A). Then, for example, in step (A), a resist film is formed on at least a part of the protective film. In this case, step (Y) is performed to remove the resist film on the protective film. In step (Y), the resist film on the protective film can be removed by a remover. At this time, similar to step (X), it is preferable to apply the remover to the front end, the peripheral end, and optionally the back end of the semiconductor manufacturing wafer. Examples of the resist remover include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, tetramethylammonium aqueous solution, or a mixture of these. Among these, propylene glycol monomethyl ether acetate and tetramethylammonium aqueous solution are preferable from the viewpoint of removability of the resist film.

[0257] After step (X) or step (Y), step (Z) of removing the protective film is performed. In step (Z), the protective film is preferably removed by ashing, or the protective film is preferably removed by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution. After that, it is preferable to wash with any solvent or a conventional semiconductor cleaning solution.

[0258] Steps (X), (Y), and (Z) can be performed simultaneously with steps (A), (B), and (C), or at any time before or after each step. For example, when step (X) is included before step (A), step (Y) of removing the resist film on the protective film can be performed between steps (A) and (B), and step (Z) of removing the protective film can be performed between steps (Y) and (B). In addition, when step (X) is included between step (A) and step (B) or step (C), step (Z) of removing the protective film can also be carried out between step (X) and step (B) or step (C).

[0259] <Process (B)> In step (B), the resist film is irradiated with light or an electron beam, and then developed to form a resist pattern.

[0260] The resist film is irradiated with light or electron beams through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used. Note that soft baking (SB) may be performed before exposure, and post-exposure baking (PEB) may be performed after exposure and before development. The temperature of post-exposure baking is preferably 50°C to 150°C, and the time of post-exposure baking is preferably 1 minute to 10 minutes.

[0261] For example, an alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C, and the development time is appropriately selected from 10 seconds to 300 seconds. As the alkaline developer, for example, an aqueous solution of an alkaline such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used. The base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10 mass%.

[0262] Furthermore, the aqueous solution of the above alkalis may be used by adding an appropriate amount of alcohols such as isopropyl alcohol, or a nonionic surfactant. Each of these may be blended in a range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like may be added to these developers.

[0263] Alternatively, instead of using an alkaline developer, development may be carried out using a polyhydric alcohol solvent having 2 to 18 carbon atoms, such as 1,2-propylene glycol, or an organic solvent, such as butyl acetate, to develop the portions of the resist where the alkaline dissolution rate is not improved.

[0264] The semiconductor substrate that has been exposed and developed is then baked. The baking method is not particularly limited, but for example, a proximity bake furnace that uses a plurality of substrate support pins to ensure a gap between the substrate and a hot plate is preferably used. The baking temperature is usually 40° C. to 300° C., preferably 200 to 300° C. for 1 to 30 minutes, but may be set to 90° C. or lower if it is necessary to avoid damage to the resist pattern.

[0265] Baking may be performed on the semiconductor substrate after exposure and before development. The baking means and conditions are as described above, but the temperature may be set to 90° C. or less if it is necessary to avoid damage to the resist pattern.

[0266] <Process (C)> In step (C), the semiconductor substrate is processed by etching using the resist pattern as a mask.

[0267] For example, the semiconductor substrate is processed by etching using the formed resist pattern as a mask. Alternatively, for example, the resist underlayer film is etched, preferably dry etched, using the formed resist pattern as a mask to form a patterned resist underlayer film. In this case, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the semiconductor substrate is processed by a method known per se (such as a dry etching method) using the patterned resist. The etching for processing the semiconductor substrate may be a known method. For example, when the semiconductor substrate is a silicon substrate, the etching method includes a process of processing the shape by dry etching using a fluorine-based gas such as carbon tetrafluoride, as well as a surface treatment process such as removing a silicon nitride film present on the surface of the semiconductor substrate with hot phosphoric acid.

[0268] Through the above steps, a semiconductor device can be manufactured.

[0269] (Method of manufacturing wafers for semiconductor manufacturing) The method for producing a wafer for semiconductor production of the present invention includes a step of applying the composition for forming a protective film of the present invention to an edge of a wafer precursor and producing a wafer whose edge is protected by the formed protective film. The protective film forming composition is applied, for example, to the edges of the wafer precursor (for example, the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the back surface edge).

[0270] The wafer precursor refers to a material obtained by subjecting a semiconductor substrate to at least one step of a method for producing a semiconductor device. For example, in the method for producing a semiconductor device as described above, the wafer precursor refers to a material that has been subjected to a step of forming an inorganic film, a resist underlayer film, a resist film, etc. on a semiconductor substrate, and is not yet subjected to a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it.

[0271] In one embodiment, the protective film forming composition of the present invention is applied by spin coating to the edges (e.g., the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the back surface edge) of a wafer precursor obtained through one or more steps of a semiconductor device manufacturing process.

[0272] The semiconductor substrate may then be heated by any suitable heating means, but for example, a proximity bake furnace that uses a plurality of substrate support pins to ensure a gap between the substrate and a hot plate is preferably used. The heating temperature is, for example, 80°C to 800°C, and preferably 150°C to 500°C. The heating time is, for example, 0.3 to 60 minutes, and preferably 0.5 to 2 minutes. After the protective film-forming composition is applied, the end face of the protective film may be subjected to known treatments in the semiconductor manufacturing process, such as edge bead removal and back rinsing.

[0273] (Wafer for semiconductor manufacturing) The wafer for semiconductor production of the present invention is a wafer for semiconductor production having a protected wafer edge, which is formed by applying the protective film-forming composition of the present invention to the wafer edge.

Claims

1. Contains a resin (G) and a solvent, The resin (G) has a composite unit structure, the composite 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 for forming 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). A composition for forming a protective film on a wafer edge in semiconductor manufacturing.

2. 2. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, wherein the unit structure (A) has 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 bonded to the aromatic ring, or does not have a heteroatom as an atom constituting the aromatic ring or an atom bonded to the aromatic ring.

3. 2. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, wherein the unit structure (B) is a unit structure derived from an aldehyde compound or an aldehyde equivalent.

4. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 3, wherein 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.

5. A protective film which is a cured product of a coating film made of the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of claims 1 to 4.

6. A semiconductor manufacturing wafer having a protected edge, the semiconductor manufacturing wafer being formed by applying a composition for forming a semiconductor manufacturing wafer edge protection film described in any one of claims 1 to 4 to the edge of a wafer precursor.

7. (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; (C) etching a semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: The method includes the step (X) of forming a protective film on an edge of a semiconductor manufacturing wafer using the composition for forming a protective film for a semiconductor manufacturing wafer according to any one of claims 1 to 4, A method for manufacturing a semiconductor device.

8. The method for manufacturing a semiconductor device according to claim 7 , wherein the step (X) is performed before the step (A).

9. The method for manufacturing a semiconductor device according to claim 7 , wherein the step (X) is performed between the step (A) and the step (B).

10. The method for manufacturing a semiconductor device according to claim 7 , wherein the step (X) is performed after the step (B) or the step (C).

11. The step (X) is carried out before the step (A); In the step (A), the resist film is formed on at least a portion of the protective film, A step (Y) of removing the resist film on the protective film; The method for manufacturing a semiconductor device according to claim 7 .

12. The method for manufacturing a semiconductor device according to claim 7 , further comprising the step (Z) of removing the protective film.

13. The method for manufacturing a semiconductor device according to claim 11, further comprising the step (Z) of removing the protective film after the step (Y).

14. 13. The method for manufacturing a semiconductor device according to claim 12, wherein the removal of the protective film in the step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning liquid for semiconductors.

15. 14. The method for manufacturing a semiconductor device according to claim 13, wherein the removal of the protective film in the step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning liquid for semiconductors.

16. A method for manufacturing a wafer for semiconductor manufacturing, comprising the steps of: A step of applying the composition for forming a wafer edge protection film for semiconductor production according to any one of claims 1 to 4 to an edge of a wafer precursor, and producing a wafer whose edge is protected by the formed protective film; A method for manufacturing a wafer for semiconductor manufacturing, comprising:

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