Compound, composition, composition for forming film for semiconductor lithography, and composition for forming resist film for semiconductor lithography

Abstract

Provided is a composition containing: a (co)polymer containing a compound represented by formula (1) and / or a constituent unit derived from a compound represented by formula (1); and at least one compound selected from the group consisting of a compound represented by formula (2), a compound represented by formula (3), and a compound represented by formula (X) [formulae (1)-(3) and formula (X) are as described in the description].

Description

Compound, composition, composition for forming film for semiconductor lithography, and composition for forming resist film for semiconductor lithography

[0001] The present invention relates to a compound, a composition, a film-forming composition for semiconductor lithography, and a resist film-forming composition for semiconductor lithography.

[0002] In recent years, advances in lithography technology have led to rapid advances in miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. A common method for miniaturizing pixels is to shorten the wavelength of the exposure light source. Specifically, while ultraviolet light, typically g-line and i-line, has traditionally been used, far-ultraviolet exposure using KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) has now become the norm for mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also increasingly being introduced. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films, such as polymethyl methacrylate, and polymeric resist materials such as polyhydroxystyrene or polyalkyl methacrylate having an acid-dissociable group (see, for example, Non-Patent Document 1 below).

[0004] Shinji Okazaki and 8 others, "40 Years of Lithography Technology," S&T Publishing, December 9, 2016

[0005] An object of the present invention is to provide a compound or the like capable of forming a film excellent in EB sensitivity, resolution, roughness, EUV sensitivity, and solid film exposure defects.

[0006] The present invention includes the following embodiments: [1] A composition comprising a compound represented by the following formula (1) and / or a (co)polymer containing a structural unit derived from the compound represented by the formula (1), and at least one compound selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (X): [In formula (1), A represents an aromatic group which may have a substituent (excluding halogen atoms) or a cyclic aliphatic group which may have a substituent (excluding halogen atoms), B represents an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent, Q represents a dissociable group, and R ０ represents a group having an unsaturated double bond, each X is independently a halogen atom, and n is an integer of 1 to 6. [In formula (2), each C1 independently represents an aromatic group which may have a substituent, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n １１ are each independently an integer of 0 to 6, and k is an integer of 0 to 6. [In formula (3), each C2 independently represents an aliphatic group which may have a substituent or an aromatic group which may have a substituent, I represents an iodine atom, and n ２２ are each independently an integer of 0 to 6, ２ are each independently a single bond or a divalent linking group, and m is an integer of 0 to 6. [In formula (X), each C1 is independently an aromatic group which may have a substituent, each C3 is independently an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and Q １ are each independently a dissociable group, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃare each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n ３３ are each independently an integer of 0 to 6, and k is an integer of 0 to 6. [2] The compound represented by formula (1) is a compound represented by formula (1-1) below: [In formula (1-1), B, Q, X, and n are as defined above, and R ｘ ~R ｚ are each independently a hydrogen atom, an aliphatic group, or a halogen atom, or R ｘ and R ｙ , or R ｙ and R ｚ may form a cyclic structure together with the carbon atoms to which they are attached, R 1 are each independently an alkoxy group or a linear, branched or cyclic monovalent group having 1 to 30 carbon atoms and not containing a polymerizable unsaturated bond, １ is an integer of 0 to 4. [3] The composition according to [1], wherein the compound represented by formula (1-1) is a compound represented by the following formula (1-2): [In formula (1-2), B, Q, X, n, R ｘ ~R ｚ , R 1 and n １ is as described above, and R ２ are each independently an alkoxy group, —OR ２Ａ OR ２Ｂ , or —OC(═O)—R ２Ｃ and R ２Ａ is an alkylene group, R ２Ｂ is an alkyl group, and R ２Ｃ is an alkoxy group, and n ２ is an integer of 1 to 4. [4] The composition according to any one of [1] to [3], wherein Q in the formula (1) contains a carbonate group, an acetal group, an ether group, or an alkyloxy group. [5] The composition according to any one of [1] to [3], wherein Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ are each independently an alkylene group optionally substituted with an alkyl group, and an asterisk * indicates a linking moiety. [5-1] The composition according to any one of [1] to [4]. [5-2] The composition according to any one of [1] to [4], wherein Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ are each independently an alkylene group optionally substituted with an alkyl group, and an asterisk * indicates a linking moiety. [6] The composition according to any one of [1] to [5]. [6] In the formula (1), Q has a structure selected from the following formulas: [6-1] The composition according to any one of [1] to [5-1], wherein Q in the formula (1) has a structure selected from the following formulas: [In the formula, the asterisk * represents a linking moiety] The composition according to any one of [1] to [6]. [7] The composition according to any one of [1] to [6-1], wherein B in the formula (1) is a benzene ring which may have a substituent or an adamantane ring which may have a substituent. [8] The composition according to any one of [1] to [7], wherein X in the formula (1) is an iodine atom. [9] The composition according to any one of [1] to [8], wherein at least one C1 in the formula (2) is a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.

[10] The composition according to any one of [1] to [9], wherein at least one C2 in the formula (3) is an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent.

[11] The composition according to any one of [1] to

[10] , wherein at least one C1 in the formula (X) is a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.

[12] The composition according to any one of [1] to

[11] , wherein the total amount of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (X) relative to the total amount of the composition is 1 ppm to 100,000 ppm.

[13] The composition according to any one of [1] to

[12] , for forming a film.

[14] The composition according to any one of [1] to

[13] , for forming a film for semiconductor lithography.

[15] The composition according to any one of [1] to

[14] , for forming a resist film for semiconductor lithography.

[16] A compound represented by the following formula (1): [In formula (1), A represents an aromatic group which may have a substituent (excluding halogen atoms) or a cyclic aliphatic group which may have a substituent (excluding halogen atoms), B represents an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent, Q represents a dissociable group, and R ０ is a group having an unsaturated double bond, X is each independently a halogen atom, and n is an integer of 1 to 6.

[17] The compound represented by formula (1) is a compound represented by the following formula (1-1): [In formula (1-1), B, Q, X, and n are as defined above, and R ｘ ~R ｚ are each independently a hydrogen atom, an aliphatic group, or a halogen atom, or R ｘ and R ｙ , or R ｙ and R ｚ may form a cyclic structure together with the carbon atoms to which they are attached, R 1 are each independently an alkoxy group or a linear, branched or cyclic monovalent group having 1 to 30 carbon atoms and not containing a polymerizable unsaturated bond, １ is an integer of 0 to 4.

[18] The compound according to

[16] , wherein the compound represented by formula (1-1) is represented by the following formula (1-2): [In formula (1-2), B, Q, X, n, R ｘ ~R ｚ , R 1 and n １ is as described above, and R ２ are each independently an alkoxy group, —OR ２Ａ OR ２Ｂ , or —OC(═O)—R ２Ｃ and R ２Ａ is an alkylene group, R ２Ｂ is an alkyl group, and R ２Ｃ is an alkoxy group, and n ２ is an integer of 1 to 4.

[19] The compound according to any one of

[16] to

[18] , wherein Q in the formula (1) contains a carbonate group, an acetal group, an ether group, or an alkyloxy group.

[20] The compound according to any one of

[16] to

[18] , wherein Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ are each independently an alkylene group optionally substituted with an alkyl group, and an asterisk * represents a linking moiety. [20-1] The compound according to any one of

[16] to

[19] . [20-2] The compound according to any one of

[16] to

[19] , wherein Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~RＱ６ are each independently an alkylene group optionally substituted with an alkyl group, and an asterisk * indicates a linking moiety.

[21] The compound according to any one of

[16] to

[20] .

[21] The compound according to any one of

[16] to

[20] , wherein Q in the formula (1) has a structure selected from the following formulas: [wherein the asterisk * represents a linking moiety] The compound according to any one of

[16] to

[20] . [21-1] In the formula (1), Q has a structure selected from the following formulas: [In the formula, the asterisk * represents a linking moiety] The compound according to any one of

[16] to

[21] .

[22] The compound according to any one of

[16] to

[21] , wherein B in formula (1) is a benzene ring which may have a substituent, or an adamantane ring which may have a substituent.

[23] The compound according to any one of

[16] to

[22] , wherein X in formula (1) is an iodine atom.

[24] A (co)polymer comprising a structural unit derived from the compound according to any one of

[16] to

[23] .

[25] A composition comprising the compound according to any one of

[16] to

[23] and / or the (co)polymer according to

[24] .

[26] The composition according to

[25] , for forming a film.

[27] The composition according to

[25] or

[26] , for forming a film for semiconductor lithography.

[28] The composition according to any one of

[25] to

[27] , for forming a resist film for semiconductor lithography.

[0007] The present invention can provide a compound capable of forming a film excellent in EB sensitivity, resolution, roughness, EUV sensitivity, and solid film exposure defects.

[0008] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these and various modifications are possible without departing from the gist of the present invention.

[0009] <Compound 1: Compound Represented by Formula (1)> One embodiment of the present invention relates to a compound represented by the following formula (1) (also referred to as "compound 1"). [In formula (1), A represents an aromatic group which may have a substituent (excluding halogen atoms) or a cyclic aliphatic group which may have a substituent (excluding halogen atoms), B represents an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent, Q represents a dissociable group, and R ０ represents a group having an unsaturated double bond, each X is independently a halogen atom, and n is an integer of 1 to 6.

[0010] A in formula (1) is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group having 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group having 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring.

[0011] A in formula (1) is preferably a cyclic aliphatic group having 4 to 30 carbon atoms which may have a substituent, more preferably a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent, even more preferably a cyclic aliphatic group having 6 to 10 carbon atoms which may have a substituent, and particularly preferably an adamantane ring which may have a substituent.

[0012] The substituent that A in formula (1) may have is not a halogen atom. Examples of the substituent that A in formula (1) may have include a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group. The substituent that A in formula (1) may have is preferably a substituent that R in formula (1-1) described below. １ is.

[0013] B in formula (1) is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group having 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group having 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring. When A in formula (1) is an optionally substituted aromatic group, it is preferable that B in formula (1) is also an optionally substituted aromatic group.

[0014] B in formula (1) is preferably a cyclic aliphatic group having 4 to 30 carbon atoms which may have a substituent, more preferably a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent, even more preferably a cyclic aliphatic group having 6 to 10 carbon atoms which may have a substituent, and particularly preferably an adamantane ring which may have a substituent. When A in formula (1) is an adamantane ring which may have a substituent, it is preferable that B in formula (1) is also an adamantane ring which may have a substituent.

[0015] The substituent that B in formula (1) may have is distinguished from X in formula (1). Examples of the substituent that B in formula (1) may have include a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group. The substituent that B in formula (1) may have is preferably a substituent that R in formula (1-2) described below. ２ is.

[0016] The dissociable group Q in formula (1) is a group that cleaves in the presence of an acid or a base to generate an alkali-soluble group (e.g., a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group), etc. Q in formula (1) is preferably an acid-dissociable group that dissociates in the presence of an acid.

[0017] The acid-dissociable group can be appropriately selected from those proposed for hydroxystyrene resins, (meth)acrylic acid resins, etc. used in chemically amplified resist compositions for KrF or ArF. Specific examples of the acid-dissociable group include those described in WO 2016 / 158168.

[0018] Q in formula (1) preferably contains a carbonate group, an acetal group, an ether group, or an alkyloxy group.

[0019] Q in formula (1) preferably has a structure selected from the following formulae: It is more preferable that Q in formula (1) has a structure selected from the following formulae: [In the formula, R Ｑ１ ~R Ｑ６ are each independently an alkylene group (preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 carbon atom) which may be substituted with an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom), and an asterisk * indicates a linking moiety.

[0020] Q in formula (1) preferably has a structure selected from the following formulae: It is more preferable that Q in formula (1) has a structure selected from the following formulae: wherein the asterisk * indicates a linking moiety.

[0021] R in formula (1) ０ is preferably —CR of the formula (1-1) described below. Ｘ =CR Ｙ R Ｚ is.

[0022] Each X in formula (1) is independently preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably an iodine atom.

[0023] In formula (1), n ​​is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

[0024] In the compound according to this embodiment, A in formula (1) does not contain an iodine atom, but B in formula (1) contains an iodine atom. By having such a structure, the compound according to this embodiment can simultaneously achieve the "sensitivity improvement effect" due to the presence of an iodine atom, or the "effect of utilizing the sensitivity improvement effect to improve lithography performance by increasing the introduction ratio of other functional moieties when designing a resist resin," and the "effect of improving development characteristics due to factors such as improved solubility in a developer of the resin after the deprotection reaction of the Q moiety in formula (1) has progressed through exposure and post-exposure bake treatment," thereby achieving both sensitivity and patterning performance such as resolution and roughness.

[0025] The compound represented by formula (1) is preferably a compound represented by the following formula (1-1): [In formula (1-1), B, Q, X, and n are as defined above, and R ｘ ~R ｚ are each independently a hydrogen atom, an aliphatic group, or a halogen atom, or R ｘ and R ｙ , or R ｙ and R ｚ may form a cyclic structure together with the carbon atoms to which they are attached, R 1 are each independently an alkoxy group or a linear, branched or cyclic monovalent group having 1 to 30 carbon atoms and containing no polymerizable unsaturated bond (this group may be substituted with at least one group selected from the group consisting of an alcohol group, an ester group, an ether group, a carbonate ester group, a carboxyl group, an amino group, a urethane, a urea, an amide group, an imide group, a thiol group and a thioester group), １ is an integer from 0 to 4.

[0026] R in formula (1-1) ｘ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0027] R in formula (1-1) ｙis preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0028] R in formula (1-1) ｚ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0029] R in formula (1-1) １ are each independently preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms.

[0030] n in formula (1-1) １ is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0031] The compound represented by formula (1-1) is preferably a compound represented by the following formula (1-2): [In formula (1-2), B, Q, X, n, R ｘ ~R ｚ , R 1 and n １ is as described above, and R ２ are each independently an alkoxy group, —OR ２Ａ OR ２Ｂ , or —OC(═O)—R ２Ｃ and R ２Ａ is an alkylene group, R ２Ｂ is an alkyl group, and R ２Ｃ is an alkoxy group, and n ２ is an integer from 1 to 4.

[0032] R in formula (1-2) ２ are each independently preferably an alkoxy group having 1 to 6 carbon atoms or —OR ２Ａ OR ２Ｂ and more preferably an alkoxy group having 1 to 4 carbon atoms or —OR ２Ａ OR ２Ｂand more preferably an alkoxy group having 1 or 2 carbon atoms or —OR ２Ａ OR ２Ｂ is.

[0033] R in formula (1-2) ２ Ga-OR ２Ａ OR ２Ｂ If R ２Ａ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, still more preferably an alkylene group having 1 or 2 carbon atoms, and particularly preferably an alkylene group having 1 carbon atom.

[0034] R in formula (1-2) ２ Ga-OR ２Ａ OR ２Ｂ If R ２Ｂ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. ２Ａ OR ２Ｂ is preferably —OCH ２ O.C. ２ H ５ or -OCH ２ OCH ３ is.

[0035] R in formula (1-2) ２ -OC(=O)-R ２Ｃ If R ２Ｃ is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms.

[0036] n in formula (1-2) ２ is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0037] Specific examples of the compound of formula (1) include the following compounds.

[0038] <Starting material composition> One embodiment of the present invention relates to a composition (also referred to as "starting material composition") containing the above-mentioned compound 1. The starting material composition may further contain at least one compound selected from the group consisting of a compound represented by the following formula (2) (also referred to as "compound 2"), a compound represented by the following formula (3) (also referred to as "compound 3"), and a compound represented by the following formula (X) (also referred to as "compound X").

[0039] From the viewpoint of improving lithography performance such as sensitivity, resolution, and roughness, the total amount of Compound 2, Compound 3, and Compound X relative to the total amount of the raw material composition is preferably 1 ppm to 100,000 ppm, more preferably 10 ppm to 50,000 ppm, and even more preferably 20 ppm to 10,000 ppm.

[0040] From the viewpoint of reducing etching defects during exposure of a solid film, the raw material composition preferably contains at least two compounds selected from the group consisting of Compound 2, Compound 3, and Compound X.

[0041] (Compound 2: Compound represented by formula (2)) The raw material composition may further contain a compound represented by the following formula (2). [In formula (2), each C1 independently represents an aromatic group which may have a substituent, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n １１ are each independently an integer of 0 to 6, and k is an integer of 0 to 6.

[0042] C1 in formula (2) is each independently preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group having 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group having 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring.

[0043] The substituent that C1 in formula (2) may have is distinguished from I bonded to C1 in formula (2). Examples of the substituent that C1 in formula (2) may have include fluorine, chlorine, bromine, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group.

[0044] R in formula (2) ａ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0045] R in formula (2) ｂ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0046] R in formula (2) ｃ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0047] X in formula (2) １ are each independently preferably a single bond, a divalent aliphatic group, an ether bond, an ester group, a carbonyl group, an amide group, an imide group, a urethane group, a urea group, an alkyleneoxy group, or an oxyalkylene group, and more preferably a single bond.

[0048] n in formula (2) １１are each independently preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2. The total number of iodine atoms in the entire formula (2) is preferably 1 to 5, and more preferably 2 to 4.

[0049] In formula (2), k is preferably 0 or 1, and more preferably 0.

[0050] Specific examples of the compound of formula (2) include the following compounds:

[0051] (Compound 3: Compound represented by formula (3)) The raw material composition may further contain a compound represented by the following formula (3). [In formula (3), each C2 independently represents an aliphatic group which may have a substituent or an aromatic group which may have a substituent, I represents an iodine atom, and n ２２ are each independently an integer of 0 to 6, ２ are each independently a single bond or a divalent linking group, and m is an integer of 0 to 6.

[0052] C2 in formula (3) is preferably a cyclic aliphatic group which may have a substituent, more preferably a cyclic aliphatic group of 4 to 30 carbon atoms which may have a substituent, even more preferably a cyclic aliphatic group of 5 to 20 carbon atoms which may have a substituent, particularly preferably a cyclic aliphatic group of 6 to 10 carbon atoms which may have a substituent, and most preferably an adamantane ring which may have a substituent.

[0053] C2 in formula (3) is each independently preferably an aromatic group of 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group of 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group of 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring.

[0054] In formula (3), some of the C2s may be aliphatic groups which may have a substituent, and the remaining C2s may be aromatic groups which may have a substituent.

[0055] The substituent that C2 in formula (3) may have is distinguished from I bonded to C2 in formula (3). Examples of the substituent that C2 in formula (3) may have include fluorine, chlorine, bromine, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group.

[0056] n in formula (3) ２２ are each independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1. The total number of iodine atoms in the entire formula (3) is preferably 0 to 3, and more preferably 1 or 2.

[0057] X in formula (3) ２ are each independently preferably a single bond, a divalent aliphatic group, an ether bond, an ester group, a carbonyl group, an amide group, an imide group, a urethane group, a urea group, an alkyleneoxy group, or an oxyalkylene group, and more preferably a single bond or an ether bond.

[0058] In formula (3), m is preferably 0 or 1, and more preferably 0.

[0059] Specific examples of the compound of formula (3) include the following compounds:

[0060] (Compound X: Compound Represented by Formula (X)) The raw material composition may further contain a compound represented by the following formula (X). [In formula (X), each C1 is independently an aromatic group which may have a substituent, each C3 is independently an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and Q １are each independently a dissociable group, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n ３３ are each independently an integer of 0 to 6, and k is an integer of 0 to 6.

[0061] C1 in formula (X) is preferably an aromatic group of 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group of 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group of 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring.

[0062] The substituent that C1 of formula (X) may have is distinguished from I bonded to C1 of formula (X). Examples of the substituent that C1 of formula (X) may have include fluorine, chlorine, bromine, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group.

[0063] Each C3 in formula (X) is independently preferably an optionally substituted cyclic aliphatic group, more preferably an optionally substituted cyclic aliphatic group having 4 to 30 carbon atoms, even more preferably an optionally substituted cyclic aliphatic group having 5 to 20 carbon atoms, particularly preferably an optionally substituted cyclic aliphatic group having 6 to 10 carbon atoms, and most preferably an optionally substituted adamantane ring.

[0064] C3 in formula (X) is preferably an aromatic group of 5 to 30 carbon atoms which may have a substituent, more preferably an aromatic group of 6 to 20 carbon atoms which may have a substituent, even more preferably an aromatic group of 6 to 10 carbon atoms which may have a substituent, particularly preferably an optionally substituted benzene ring or an optionally substituted naphthalene ring, and most preferably an optionally substituted benzene ring.

[0065] The substituent that C3 of formula (X) may have is distinguished from I bonded to C3 of formula (X). Examples of the substituent that C3 of formula (X) may have include fluorine, chlorine, bromine, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, a hydroxyalkyl group, and an alkoxyalkyloxy group.

[0066] The dissociable group Q of formula (X) １ is a group that is cleaved in the presence of an acid or a base to generate an alkali-soluble group (e.g., a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group), etc. １ is preferably an acid-dissociable group that dissociates with an acid.

[0067] The acid-dissociable group can be appropriately selected from those proposed for hydroxystyrene resins, (meth)acrylic acid resins, etc. used in chemically amplified resist compositions for KrF or ArF. Specific examples of the acid-dissociable group include those described in WO 2016 / 158168.

[0068] Q in formula (X) １ preferably contains a carbonate group, an acetal group, an ether group, or an alkyloxy group.

[0069] Q in formula (X) １Preferably, has a structure selected from the following formulas: Q in formula (X) １ More preferably, has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ are each independently an alkylene group (preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 carbon atom) which may be substituted with an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom), and an asterisk * indicates a linking moiety.

[0070] Q in formula (X) １ Preferably, has a structure selected from the following formulas: Q in formula (X) １ More preferably, has a structure selected from the following formulas: wherein the asterisk * indicates a linking moiety.

[0071] R in formula (X) ａ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0072] R in formula (X) ｂ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0073] R in formula (X) ｃ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0074] X in formula (X) １ are each independently preferably a single bond, a divalent aliphatic group, an ether bond, an ester group, a carbonyl group, an amide group, an imide group, a urethane group, a urea group, an alkyleneoxy group, or an oxyalkylene group, and more preferably a single bond.

[0075] n in formula (X) ３３are each independently preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2. The total number of iodine atoms in the entire formula (X) is preferably 1 to 5, and more preferably 2 to 4.

[0076] In formula (X), k is preferably 0 or 1, and more preferably 0.

[0077] Specific examples of the compound of formula (X) include the following compounds.

[0078] In the above compound, Pro represents the following structure:

[0079] <(Co)polymer> One embodiment of the present invention relates to a (co)polymer containing a structural unit derived from Compound 1. The (co)polymer of this embodiment may further contain a structural unit derived from at least one compound selected from the group consisting of Compound 2, Compound 3, and Compound X. Furthermore, Compound 2, Compound 3, and Compound X may be present in the vicinity of the (co)polymer without being incorporated into the (co)polymer.

[0080] The (co)polymer of the present embodiment may contain further structural units. Examples of the further structural units include structural units derived from the compounds described below and the structural units described below. 2-ethyl-2-adamantyl methacrylate (EAMA), γ-butyrolactone methacrylic acid ester (GMA), 4-hydroxy-vinylphenyl; those described in International Publication WO 2016 / 125782, International Publication WO 2015 / 115613, JP 2015 / 117305, International Publication WO 2014 / 175275, and JP 2012 / 162498; commercially available products, such as γ-butyrolactone (meth)acrylate (trade names: GBLA, GBLMA), adamantyl-based monomers (MADA, MADMA, EtADA, EAMA(P)), monomers having a phenolic hydroxyl group (HQMA, HMAd, isobornyl methacrylate (IBOMA)), manufactured by Osaka Organic Chemical Industry, Ltd.; and compounds represented by the following formula (C1) and formula (C2).

[0081] (In formula (C1), R Ｃ１１ represents a hydrogen atom or a methyl group; R Ｃ１２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R Ｃ１３ is R Ｃ１３ represents a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms together with the carbon atom to which it is attached, and the dot * represents the bonding point to the adjacent repeating unit. Preferably, R Ｃ１２ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R Ｃ１３ is R Ｃ１３ R is, together with the carbon atom to which it is attached, a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms. １３ may have a substituent (for example, an oxo group).

[0082] (In formula (C2), R Ｃ２１ represents a hydrogen atom or a methyl group; R Ｃ２２ and R Ｃ２３ each independently represents an alkyl group having 1 to 4 carbon atoms; Ｃ２４ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms; R Ｃ２２ ~R Ｃ２４ Two or three of these may form an alicyclic structure having 3 to 20 carbon atoms together with the carbon atoms to which they are attached, and the dot * indicates the bonding point to the adjacent repeating unit.) Preferably, R Ｃ２２ represents an alkyl group having 1 to 3 carbon atoms, and R Ｃ２４ is a cycloalkyl group having 5 to 10 carbon atoms. Ｃ２２ ~R Ｃ２４ The alicyclic structure formed by may contain multiple rings such as an adamantyl group, etc. The alicyclic structure may have a substituent (e.g., a hydroxyl group, an alkyl group).

[0083] Examples of the monomer raw material for the structural unit represented by the above formula (C2) include 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl-1- (meth)acryloyloxycyclohexane, 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl-1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclooctane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl-2-(meth)acryloyloxydecahydro-1,4:5,8-dimethanonaphthalene, and 2-ethyl-2-(meth)acryloyloxynorbornane.

[0084] From the viewpoint of improving lithography performance such as sensitivity, resolution, and roughness, the amount of the structural units derived from Compound 1 contained in the (co)polymer is preferably 1 to 90 mol %, more preferably 5 to 70 mol %, even more preferably 10 to 50 mol %, and particularly preferably 20 to 40 mol %, based on the total number of moles of all structural units constituting the (co)polymer.

[0085] The method for synthesizing the (co)polymer of this embodiment is not particularly limited, and any known polymerization method can be used. The obtained (co)polymer may be purified by a known method.

[0086] <Film-forming composition> One embodiment of the present invention relates to a film-forming composition containing the above-mentioned compound 1, raw material composition, or (co)polymer.

[0087] The film-forming composition may further contain a base material (A), a solvent (S), an acid generator (C), a base generator (G), an acid diffusion controller (E), other components (F), and the like, which will be described later.

[0088] [Substrate (A)] "Substrate (A)" refers to a substrate (e.g., a substrate for lithography or a substrate for resist) that is used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB). Any of these substrates can be used as the substrate (A) without any particular limitation. Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, from the viewpoint of the shape of the resulting resist pattern, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.

[0089] The derivative is not particularly limited, but examples thereof include those into which a dissociable group has been introduced, those into which a crosslinkable group has been introduced, etc. The derivative into which a dissociable group or a crosslinkable group has been introduced can undergo a dissociation reaction or a crosslinking reaction by the action of light, acid, etc.

[0090] The term "dissociable group" refers to a characteristic group that cleaves to generate a functional group such as an alkali-soluble group that changes solubility. The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. The phenolic hydroxyl group and the carboxyl group are preferred, and the phenolic hydroxyl group is particularly preferred.

[0091] The term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples thereof include an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinyl-containing phenylmethyl group.

[0092] [Solvent (S)] Specific examples of the solvent (S) include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-butyl lactate, lactic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; aliphatic carboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and 3-methoxy-3-methylpropionate. aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactone.The solvent (S) is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0093] The amounts of the solid component and the solvent (S) are not particularly limited, but are preferably 1 to 80 mass% of the solid component and 20 to 99 mass% of the solvent, more preferably 1 to 50 mass% of the solid component and 50 to 99 mass% of the solvent, even more preferably 2 to 40 mass% of the solid component and 60 to 98 mass% of the solvent, and particularly preferably 2 to 10 mass% of the solid component and 90 to 98 mass% of the solvent, relative to the total mass of the solid component and the solvent (S). In this specification, the term "solid component" refers to components other than the solvent contained in the composition of the present embodiment.

[0094] [Acid Generator (C)] The acid generator (C) generates an acid directly or indirectly when irradiated with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. Examples of the acid generator (C) include those described in International Publication WO2013 / 024778.

[0095] The amount of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, of the total mass of the solid components. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained. The method for generating the acid is not particularly limited, as long as an acid is generated in the system. Using an excimer laser instead of ultraviolet light such as g-line or i-line enables finer processing, and using an electron beam, extreme ultraviolet light, X-ray, or ion beam as a high-energy beam enables even finer processing.

[0096] [Base Generator (G)] Examples of the base generator (G) include a photobase generator, which generates a base upon exposure to light and is inactive under normal conditions of room temperature and normal pressure, but generates a base (basic substance) upon exposure to electromagnetic waves and heating as external stimuli.

[0097] Examples of photobase generators include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0098] Examples of basic substances generated from the photobase generator include compounds having an amino group (particularly monoamines), polyamines such as diamines, and amidines.

[0099] From the viewpoint of sensitivity and resolution, it is preferable that the generated basic substance is a compound having an amino group with a higher basicity (a conjugate acid with a higher pKa value).

[0100] Examples of the photobase generator include base generators having a cinnamic acid amide structure as disclosed in JP 2009-80452 A and WO 2009 / 123122 A, base generators having a carbamate structure as disclosed in JP 2006-189591 A and JP 2008-247747 A, base generators having an oxime structure or a carbamoyloxime structure as disclosed in JP 2007-249013 A and JP 2008-003581 A, and compounds described in JP 2010-243773 A, but are not limited to these, and other known base generator structures can also be used.

[0101] The amount of the base generator (G) is preferably from 0.001 to 49% by mass, more preferably from 1 to 40% by mass, even more preferably from 3 to 30% by mass, and particularly preferably from 10 to 25% by mass, based on the total mass of the solid components.

[0102] [Acid Diffusion Controller (E)] The acid diffusion controller (E) has the effect of controlling the diffusion of the acid generated from the acid generator by irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed areas. Use of the acid diffusion controller (E) tends to improve the storage stability of the composition of this embodiment. Furthermore, use of the acid diffusion controller (E) tends to improve the resolution of the film formed using the composition of this embodiment, and also tends to suppress changes in the line width of the resist pattern due to variations in the waiting time before and after irradiation, resulting in excellent process stability.

[0103] The acid diffusion controller (E) is not particularly limited, but examples thereof include radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds. The acid diffusion controller (E) is not particularly limited, but examples thereof include those described in International Publication WO2013 / 024778.

[0104] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, based on the total mass of the solid components. When the amount of the acid diffusion controller (E) is within this range, degradation of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, degradation of the shape of the upper layer of the pattern can be suppressed. Furthermore, when the blending amount is 10% by mass or less, degradation of sensitivity, developability of unexposed areas, and the like tends to be prevented. Furthermore, the use of such an acid diffusion controller improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in exposure time before and after radiation exposure, tending to result in excellent process stability.

[0105] [Other Components (F)] The composition of the present embodiment may optionally contain one or more of various additives as other components (F), such as a crosslinker, a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof. Specific components and amounts thereof are described, for example, in paragraphs

[0210] to

[0226] of WO 2024 / 005049.

[0106] <Method of Using the Film-Forming Composition> To form a resist pattern from the film-forming composition, for example, a solution of the composition is applied to a substrate such as a silicon wafer, metal, plastic, glass, or ceramic using an appropriate coating means such as a spin coater, dip coater, or roller coater to form a resist film, which may be optionally pre-heat-treated at a temperature of about 50°C to 200°C and then exposed through a predetermined mask pattern. The thickness of the coating film is, for example, about 0.1 to 20 μm, preferably about 0.3 to 2 μm. Light rays of various wavelengths, such as ultraviolet rays and X-rays, can be used for exposure. For example, light sources such as far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, and electron beams can be appropriately selected.

[0107] In order to stably form a highly accurate fine pattern, it is preferable to carry out a heat treatment after exposure at a temperature of 50 to 200°C for 30 seconds or more. In this case, if the temperature is less than 50°C, there is a risk of widening the variation in sensitivity depending on the type of substrate. Thereafter, the resist is developed with an alkaline developer typically at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds, to form a predetermined resist pattern.

[0108] The alkaline developer may be, for example, an alkaline aqueous solution prepared by dissolving an alkaline compound such as an alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene to a concentration of typically 1 to 10% by weight, preferably 1 to 3% by weight. A water-soluble organic solvent or a surfactant may also be added to the alkaline aqueous developer, as appropriate.

[0109] <Uses of Film-Forming Composition> The film-forming composition can be preferably used to form a film for semiconductor lithography, and more preferably to form a resist film for semiconductor lithography. The film-forming composition can be used to form an upper layer film, an intermediate layer, or an underlayer film. These can primarily or supplementarily perform optical or electromagnetic radiation functions such as anti-reflection and prevention of secondary electron diffusion, and pattern quality improvement functions such as preventing pattern collapse and defects due to chemical and physical effects, and maintaining the pattern shape, for the purpose of improving the patterning performance of the resist layer in the lithography process. The film-forming composition can form a film with high sensitivity and can also impart a good resist pattern shape.

[0110] The film-forming composition can also be used as an optical component-forming composition that applies lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on photodiodes, planarizing films before and after color filters, microlenses, and planarizing and conformal films on microlenses, which are components of solid-state imaging elements that require a high refractive index.

[0111] The present invention will be described in more detail below using examples and comparative examples, but the technical scope of the present invention is not limited to these.

[0112] [Measurement Method] The structure of the compound was measured using a Bruker Advance 600II spectrometer under the following conditions: １ The product was confirmed by H-NMR measurement. Frequency: 6400 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: TMS Measurement temperature: 23 ° C. Also, １３ C-NMR measurement was carried out using the same apparatus under the following conditions: Frequency: 150 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: Use the solvent used Measurement temperature: 23°C

[0113] <Synthesis of Compound A: Corresponding to the Compound of Formula (1)> [Synthesis Example A1: Synthesis of Compound A1]

[0114] (Step 1: Iodination Step) A 100 L glass-lined reaction vessel connected to a reflux condenser was charged with 700 g of salicylaldehyde, 5700 ml of ethanol, and 1164 g of iodine. Under a nitrogen flow, the vessel was heated in a water bath to an internal temperature of 40°C, and stirred at 220 rpm for 1 hour to dissolve the contents. 2490 g of a 20% by mass aqueous iodic acid solution was then slowly added dropwise over 60 minutes. The internal temperature was then raised to 50°C, and stirring was continued for 2 hours. Next, 2.3 L of a 20% by mass aqueous sodium sulfite solution was added with stirring, followed by the addition of 7.6 L of pure water. The precipitate formed was collected by filtration. After rinsing with 5 L of pure water, the mixture was dried to obtain 2-hydroxy-3,5-diiodobenzaldehyde (2046 g) in a yield of 95.5%.

[0115] (Step 2: Protecting Group Introduction Step) Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 1822 g of 2-hydroxy-3,5-diiodobenzaldehyde was added to 3650 mL of dehydrated dimethylformamide (DMF) in an ice bath under nitrogen flow and stirred with a stirring blade until dissolved. Next, 673 g of potassium carbonate (1.0 equivalent relative to the substrate) was added while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 553 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution using a dropping funnel over 60 minutes, and the mixture was stirred for an additional 30 minutes in the ice bath. Subsequently, 7.2 L of purified water was added in the ice bath, and after stirring for 60 minutes, the formed precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in the ice bath for 30 minutes, and then filtered to obtain the desired protected compound as a white solid (1936 g). The yield was 92%.

[0116] (Step 3: Reduction Step) A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 2,450 g of the protected compound obtained in the previous step was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 5 L of pure water. The resulting precipitate was dissolved in 10.5 L of ethyl acetate and washed three times with 3.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and then dried to obtain 2092 g of an alcohol with a yield of 85% and an LC purity of 98%.

[0117] (Step 4: Vinyl Etherification Step) A 10 L four-neck flask was used, and a reflux condenser and Dean-Stark tube were connected. 21.7 g (50 mmol) of the alcohol, 8.1 g (100 mmol) of 2-chloroethanol, and 0.63 g (2.5 mmol) of pyridinium p-toluenesulfonate were added to 50 mL of toluene so that the alcohol concentration was 1 mol / L. The mixture was refluxed for 16 hours. Approximately 50 mmol of HO was recovered during this process. The reaction mixture was then cooled to room temperature, and a separation and washing operation was performed using 50 mL of pure water. The aqueous phase was discarded. Separation and washing was performed twice using 25 mL of 0.1 M aqueous NaOH solution, and then another separation and washing operation was performed using 50 mL of pure water. 10 g of magnesium sulfate was added to the recovered organic phase, which was stirred for 6 hours. The organic phase was then recovered by filtration and further purified using a short-path column with 30 g of silica gel (C-60N, manufactured by Kanto Chemical Co., Inc.). The recovered organic phase was concentrated and dried to obtain 18.6 g (yield 81%) of the target product (vinyl ether compound).

[0118] (Step 5: Acetalization Step) To 50 mL of vinylphenol (10% propylene glycol solution), 200 mL of water and 50 mL of toluene were added under ice-cooling at 4°C. The mixture was stirred for 30 minutes, and the organic phase was recovered to obtain a 10% vinylphenol toluene solution. A 100 mL three-neck flask was prepared, and 50 mL of toluene and 50 mL of the prepared vinylphenol toluene solution were added under ice-cooling. Furthermore, 18.6 g of the vinyl ether prepared in (Step 4) was dissolved in toluene to prepare a vinyl ether toluene solution, which was then gradually added to the prepared 100 mL flask. After adding 1.0 g of pyridinium p-toluenesulfonate (0.1 equivalent relative to vinylphenol), stirring was continued for 10 hours. Subsequently, 0.4 g of triethylamine (0.11 equivalent) and 50 mL of pure water were added, and the mixture was stirred for 30 minutes. After adding 50 mL of ethyl acetate, the organic phase was recovered. The organic phase was concentrated to obtain a crude product, which was then passed through a short-path column using silica gel (C60N manufactured by Dry Chemical Industry Co., Ltd.) and a developing solvent (hexane / ethyl acetate=9 / 1), and then further passed through a short-path column using NH silica (developing solvent hexane / ethyl acetate=9 / 1). The recovered organic phase was concentrated to obtain compound A1 (18.8 g).

[0119] [Synthesis Example A2: Synthesis of Compound A2]

[0120] Compound A2 was obtained in the same manner as in Synthesis Example A1, except that the starting material in Synthesis Example A1 was changed to 4-hydroxybenzaldehyde.

[0121] [Synthesis Example A3: Synthesis of Compound A3]

[0122] (Iodination Step) A 5 L separable flask equipped with a Dean-Stark tube was charged with 105.6 g of adamantanetriol (ADT) and 3,333 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 400.0 g of 55% hydroiodic acid was added while stirring at a stirring speed of 70 rpm using a blade with a length approximately half the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases, a toluene phase and an aqueous phase, but was homogeneous with no residual raw materials. During the reaction, the amount of distillate withdrawn was determined every two hours, and the distillate was withdrawn. After 8 hours from the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was stopped by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of DIADOH (3,5-diiodoadamantan-1-ol) was dissolved in the toluene phase, and 1,3,5-triiodoadamantane was not produced. The reaction solution was cooled to 34°C, and 1667 mL of water was added. Thereafter, a 10% aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. The amount of 10% aqueous sodium sulfite solution used was 4.0 mL. After removing the aqueous phase by separation, 1667 mL of water was added, and stirring and separation were performed. The toluene phase was concentrated using a rotary evaporator. After concentration, a slurry state was obtained, and the mass was 279.9 g. The slurry was filtered, and the separated crystals were dried under reduced pressure, yielding DIADOH with a GC area percentage of 99.1% and an isolation yield of 94.8%.

[0123] (Vinyl Etherification Step) A 10 L four-neck flask was used, and a reflux condenser and Dean-Stark tube were connected. 20.2 g of DIADOH (alcohol form, 50 mmol), 8.1 g (100 mmol) of 2-chloroethanol, and 0.63 g (2.5 mmol) of pyridinium paratoluenesulfonate were charged into 50 mL of toluene so that the alcohol concentration was 1 mol / L, and reflux was carried out for 16 hours. During this process, approximately 50 mmol of HO was recovered. The reaction solution was then cooled to room temperature, and a separation and washing operation was carried out using 50 mL of pure water, and the aqueous phase was discarded. Separation and washing was carried out twice using 25 mL of 0.1 M aqueous NaOH solution, and then a separation and washing operation was carried out using 50 mL of pure water. 10 g of magnesium sulfate was added to the recovered organic phase, and the mixture was stirred for 6 hours. The organic phase was then recovered by filtration and further purified using a short-path column with 30 g of silica gel (C-60N, manufactured by Kanto Chemical Co., Inc.). The recovered organic phase was concentrated and dried to obtain 17.6 g (yield 81%) of the target product (vinyl ether).

[0124] (Acetalization Step) To 50 mL of vinylphenol (10% propylene glycol solution), 200 mL of water and 50 mL of toluene were added under ice cooling at 4°C. The mixture was stirred for 30 minutes, and the organic phase was recovered to obtain a 10% vinylphenol toluene solution. A 100 mL three-neck flask was prepared, and 50 mL of toluene and 50 mL of the prepared vinylphenol toluene solution were added under ice cooling. Furthermore, 17.6 g of the vinyl ether compound prepared in the (vinyl etherification step) was dissolved in toluene to prepare a vinyl ether toluene solution, which was then gradually added to the prepared 100 mL flask. After adding 1.0 g of pyridinium paratoluenesulfonate (0.1 equivalents relative to vinylphenol), stirring was continued for 10 hours. Subsequently, 0.4 g of triethylamine (0.11 equivalents) and 50 mL of pure water were added, and the mixture was stirred for 30 minutes. After adding 50 mL of ethyl acetate, the organic phase was recovered. The organic phase was concentrated to obtain a crude product, which was then passed through a short-path column using silica gel (C60N manufactured by Dry Chemical Industry Co., Ltd.) and a developing solvent (hexane / ethyl acetate=9 / 1), and then further passed through a short-path column using NH silica (developing solvent hexane / ethyl acetate=9 / 1). The recovered organic phase was concentrated to obtain compound A3 (17.8 g, yield 80%).

[0125] [Synthesis Example A4: Synthesis of Compound A4]

[0126] Compound A4 was obtained in the same manner as in Synthesis Example A1, except that the starting material in Synthesis Example A1 was changed to vanillin and the amount of iodinating agent in the iodination step was increased to 1 / 2.

[0127] [Synthesis Example A5: Synthesis of Compound A5]

[0128] Compound A5 was obtained in the same manner as in Synthesis Example A1, except that the starting material in Synthesis Example A1 was changed to ethyl vanillin and the amount of iodinating agent in the iodination step was increased to 1 / 2.

[0129] [Synthesis Example A6: Synthesis of Compound A6]

[0130] (Alkylation of hydroxystyrene) Synthesis of 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate Under light-blocking conditions (an environment in which light with a wavelength of 500 nm or less was dimmed under a yellow lamp (trade name: fluorescent lamp with shatterproof film for semiconductor factories, pure yellow (FLR40SYFMP), manufactured by Panasonic Corporation)), a 300 mL three-neck flask was prepared, and 100 mL of acetone, 8.0 g (20.8 mmol) of commercially available 2-(4-iodophenyl)propan-2-yl 2-bromoacetate, 2.5 g (20.8 mmol), 2.9 g (20.8 mmol) of potassium carbonate, and 0.55 g (2.08 mmol) of 18-crown-6 were added. The contents were stirred under reflux under a nitrogen flow for 3 hours. After ice-cooling to an internal temperature of 10°C or less, 50 g of ion-exchanged water was added dropwise over 20 minutes, and then 80 g of toluene was added. The mixture was stirred for 15 minutes and allowed to stand, after which the aqueous layer was removed. Further, 50 g of ion-exchanged water was added, and the mixture was stirred for 15 minutes, then allowed to stand and the aqueous layer was removed. This procedure was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled out, yielding a crude product. The crude product was purified using a silica gel column to yield the target compound, 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate (7.6 g, 17.9 mmol). １ H-NMR (500MHz, DMSO-d6) δ7.71 (2H, Ph), 7.36 (2H, Ph), 7.12 (2H, Ph), 6.88 (2H, Ph), 6.62 (1H, CH ２ =CH-Ph), 5.65(1H,CH ２ =CH-Ph), 5.12(1H,CH ２ =CH-Ph), 4.54(2H, PhO-CH ２ -), 1.69 (6H, -CH ３ )

[0131] [Synthesis Example A7: Synthesis of Compound A7]

[0132] Synthesis of 2-(4-iodo-3-methoxyphenyl)propan-2-yl 2-bromoacetate 2-(4-iodo-3-methoxyphenyl)propan-2-yl 2-bromoacetate was obtained in the same manner as in the synthesis of 2-(4-iodo-3-methylphenyl)propan-2-yl 2-bromoacetate, using 2-(4-iodo-3-methoxyphenyl)propan-2-ol obtained by the method described in Org. Lett. 2021, 23, 3755-3760. １ H-NMR (500MHz, DMSO-d6) δ7.75 (1H, Ph), 7.31 (1H, Ph), 6.98 (1H, Ph), 3.82 (3H, -OCH ３ ), 3.68 (2H, Br-CH ２ -), 1.65 (6H, -CH ３ )

[0133] Synthesis of 2-(4-iodo-3-methoxyphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate 2-(4-Iodo-3-methoxyphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate. １ H-NMR (500MHz, DMSO-d6) δ7.75 (1H, Ph), 7.36-7.34 (3H, Ph), 6.95-6.90 (3H, Ph), 6.65 (1H, CH ２ =CH-Ph), 5.62 (1H, CH ２ =CH-Ph), 5.14 (1H, CH2=CH-Ph), 4.51 (2H, PhO-CH ２ -), 3.65 (3H, -OCH ３ ), 1.65 (6H, -CH ３ )

[0134] [Synthesis Example A8: Synthesis of Compound A8]

[0135] (Acylation of tertiary alcohol) Synthesis of 2-(4-iodo-3-methylphenyl)propan-2-yl 2-bromoacetate Under light-blocking conditions (an environment in which light with a wavelength of 500 nm or less was reduced under a yellow lamp (manufactured by Panasonic Corporation, trade name: fluorescent lamp with anti-scattering film for semiconductor factories <pure yellow> (FLR40SYFMP))), a 300 mL three-neck flask was prepared, and 72 mL of dehydrated THF, 10 g of 2-(4-iodo-3-methylphenyl)propan-2-ol (36.2 mmol, synthesized by the method described in J. Am. Chem. Soc. 2015, 137, 3775-3778), and 3.6 g of pyridine (45.2 mmol) were added, and the flask was stirred for 30 minutes under a nitrogen flow while cooling on ice so that the internal temperature was 10°C or less. A solution of 9.1 g (45.2 mmol) of bromoacetyl bromide in 15 mL of THF was added to a 300 mL three-neck flask over 20 minutes, and the internal temperature was then returned to 25°C over 15 minutes. Stirring was continued for 72 hours. After ice-cooling to keep the internal temperature below 10°C, 50 g of ion-exchanged water was added dropwise over 20 minutes, followed by an additional 80 g of toluene. The mixture was stirred for 15 minutes, allowed to stand, and then the aqueous layer was drained. This procedure of adding 50 g of ion-exchanged water, stirring for 15 minutes, allowing to stand, and draining the aqueous layer was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no solvent components were distilled out, yielding a crude product. The crude product was purified using a silica gel column to yield the target compound, 2-(4-iodo-3-methylphenyl)propan-2-yl 2-bromoacetate (10.0 g, 25.3 mmol). １ H-NMR (500MHz, DMSO-d6) δ7.75 (1H, Ph), 7.32 (1H, Ph), 6.97 (1H, Ph), 3.72 (2H, Br-CH ２ -), 2.42 (3H, Ph-CH ３ ), 1.68 (6H, -CH ３ )

[0136] Synthesis of 2-(4-iodo-3-methylphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate 2-(4-iodo-3-methylphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate. １H-NMR (500MHz, DMSO-d6) δ7.72 (1H, Ph), 7.36-7.34 (3H, Ph), 6.95-6.90 (3H, Ph), 6.65 (1H, CH ２ =CH-Ph), 5.63(1H,CH ２ =CH-Ph), 5.15(1H,CH ２ =CH-Ph), 4.52 (2H, PhO-CH ２ -), 2.41 (3H, Ph-CH ３ ), 1.68 (6H, -CH ３ )

[0137] [Synthesis Example A9: Synthesis of Compound A9]

[0138] (Protector synthesis) Under light-blocking conditions (an environment in which light with a wavelength of 500 nm or less was dimmed under a yellow lamp (manufactured by Panasonic Corporation, product name: fluorescent lamp with anti-scattering film for semiconductor factories, pure yellow (FLR40SYFMP))), a 200 mL three-neck flask was prepared, and under a nitrogen flow, 5.6 g (20 mmol) of methyl 4-hydroxy-3-iodobenzoate (purchased from Sigma-Aldrich), 50 mL of toluene, 14.5 g (200 mmol) of ethyl vinyl ether, and 1.8 g (7.0 mmol) of pyridinium p-toluenesulfonate (PPTS) were added, and the mixture was stirred at an internal temperature of 25°C for 5 hours. Thereafter, 0.79 g (7.7 mmol) of triethylamine and 50 g of ion-exchanged water were added, and the mixture was stirred for 15 minutes and allowed to stand, after which the organic layer was recovered. The recovered organic layer was concentrated until no solvent components were distilled out, yielding a crude product. The resulting crude product was purified through a column using silica gel to obtain the target compound, methyl 4-(1-ethoxyethoxy)-3-iodobenzoate (6.5 g, 18.6 mmol). １ H-NMR (500MHz, DMSO-d6) δ8.37 (1H, Ph), 7.86 (1H, Ph), 6.93 (1H, Ph), 5.53 (1H, O-CH-O), 3.84 (3H, O-CH ３ ), 3.72 (1H, O-CH ２ -CH ３ ), 3.65 (1H, O-CH ２ -CH ３), 1.61 (3H, -CH-CH3), 1.13 (3H, -CH ２ -CH ３ )

[0139] Synthesis of 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-ol This was obtained in the same manner as in the synthesis of 2-(3,5-diiodo-4-methoxyphenyl)propan-2-ol. １ H-NMR (500MHz, DMSO-d6) δ7.82 (1H, Ph), 7.45 (1H, Ph), 6.86 (1H, Ph), 5.51 (1H, O-CH-O), 5.05 (1H, OH), 3.74 (1H, O-CH ２ -CH ３ ), 3.66 (1H, O-CH ２ -CH ３ ), 1.61 (3H, -CH-CH ３ ), 1.32 (6H, -CH ３ ). 1.13(3H, -CH ２ -CH ３ )

[0140] Synthesis of 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-yl 2-bromoacetate 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-yl 2-bromoacetate was obtained in the same manner as in the synthesis of 2-(4-iodo-3-methylphenyl)propan-2-yl 2-bromoacetate. １ H-NMR (500MHz, DMSO-d6) δ7.82 (1H, Ph), 7.45 (1H, Ph), 6.88 (1H, Ph), 5.52 (1H, O-CH-O), 3.74 (1H, O-CH ２ -CH ３ ), 3.70 (2H, Br-CH ２ -), 3.65 (1H, O-CH ２ -CH ３ ), 1.70 (6H, -CH ３ ), 1.61 (3H, -CH-CH ３ ), 1.15 (3H, -CH ２ -CH ３ )

[0141] Synthesis of 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate. １ H-NMR (500MHz, DMSO-d6) δ7.81 (1H, Ph), 7.45 (1H, Ph), 7.34 (2H, Ph), 6.90-6.87 (3H, Ph), 6.62 (1H, CH ２ =CH-Ph), 5.62 (1H, CH ２ =CH-Ph), 5.51 (1H, O-CH-O). 5.12 (1H, CH ２ =CH-Ph), 4.52 (2H, PhO-CH ２ -), 3.75 (1H, O-CH ２ -CH ３ ), 3.64 (1H, O-CH2-CH ３ ), 1.68 (6H, -CH ３ ), 1.62 (3H, -CH-CH ３ ), 1.18 (3H, -CH ２ -CH ３ )

[0142] (Hydrolysis of ethoxyethyl group) Synthesis of 2-(4-hydroxy-3-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate Under light-blocking conditions (an environment in which light with a wavelength of 500 nm or less was dimmed under a yellow lamp (manufactured by Panasonic Corporation, product name: fluorescent lamp with anti-scattering film for semiconductor factories, pure yellow (FLR40SYFMP))), a 300 mL three-neck flask was prepared, and under a nitrogen flow, 5.2 g (10 mmol) of 2-(4-(1-ethoxyethoxy)-3-iodophenyl)propan-2-yl 2-)4-vinylphenoxy)acetate, 50 mL of methanol, and 0.26 g (1.0 mmol) of pyridinium p-toluenesulfonate (PPTS) were added, and the mixture was stirred at an internal temperature of 25°C for 2 hours. Thereafter, 50 g of ion-exchanged water and 80 g of toluene were added, and the mixture was stirred for 15 minutes and allowed to stand, after which the organic layer was recovered. The recovered organic layer was concentrated until no solvent components were distilled out, yielding a crude product. The resulting crude product was purified through a column using silica gel to obtain the target compound, 2-(4-hydroxy-3-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate (4.2 g, 9.5 mmol). １ H-NMR (500MHz, DMSO-d6) δ9.45 (1H, Ph-OH), 7.81 (1H, Ph), 7.45 (1H, Ph), 7.34 (2H, Ph), 6.90-6.87 (3H, Ph), 6.62 (1H, CH ２ =CH-Ph), 5.62 (1H, CH ２ =CH-Ph), 5.12(1H,CH ２ =CH-Ph), 4.52 (2H, PhO-CH ２ -), 1.68 (6H, -CH ３ )

[0143] [Synthesis Example A10: Synthesis of Compound A10]

[0144] (Tertiary alcohol synthesis) Synthesis of 2-(3,5-diiodo-4-methoxyphenyl)propan-2-ol Under light-blocking conditions (an environment in which light with a wavelength of 500 nm or less was reduced under a yellow lamp (manufactured by Panasonic Corporation, product name: fluorescent lamp with anti-scattering film for semiconductor factories <pure yellow> (FLR40SYFMP))), a 300 mL three-neck flask was prepared, and 36 mL of dehydrated THF and 15.2 g of methyl 3,5-diiodo-4-methoxybenzoate (36.2 mmol, synthesized by the method described in J. Am. Chem. Soc. 2020, 142, 8728-8737) were added, followed by stirring for 30 minutes under a nitrogen flow while cooling on ice so that the internal temperature was 10°C or less. 90.5 mL (90.5 mmol, 1.0 M THF solution) of methyl magnesium bromide (nucleophile: Grignard reagent) was added to a 300 mL three-neck flask over 20 minutes, and the internal temperature was returned to 25 ° C. over 15 minutes, then the internal temperature was increased to 50 ° C. over 20 minutes, and stirring was continued for 120 minutes. After ice cooling so that the internal temperature was 10 ° C. or less, 90 g of saturated aqueous ammonium chloride solution was added dropwise over 20 minutes, and then 52 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Furthermore, 40 g of ion-exchanged water was added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. This operation was repeated three times. The recovered organic layer was concentrated by distillation under reduced pressure until no solvent components were distilled out, and a crude product was obtained. The resulting crude product was purified by column chromatography using silica gel to obtain the target compound, 2-(3,5-diiodo-4-methoxyphenyl)propan-2-ol (14.3 g, 34.2 mmol). １ H-NMR (500MHz, DMSO-d6) δ7.83 (2H, Ph), 5.10 (1H, OH), 3.84 (3H, O-CH ３ ), 1.35 (6H, -CH ３ )

[0145] Synthesis of 2-(3,5-diiodo-4-methoxyphenyl)propan-2-yl 2-bromoacetate 2-(3,5-Diiodo-4-methoxyphenyl)propan-2-yl 2-bromoacetate was obtained in the same manner as in the synthesis of 2-(4-iodo-3-methylphenyl)propan-2-yl 2-bromoacetate. １ H-NMR (500MHz, DMSO-d6) δ7.80 (2H, Ph), 3.81 (3H, O-CH ３), 3.74 (2H, Br-CH ２ -), 1.65 (6H, -CH ３ )

[0146] Synthesis of 2-(3,5-diiodo-4-methoxyphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate 2-(3,5-Diiodo-4-methoxyphenyl)propan-2-yl 2-(4-vinylphenoxy)acetate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl 2-(4-vinylphenoxy)acetate. １ H-NMR (500MHz, DMSO-d6) δ7.80 (2H, Ph), 7.36 (2H, Ph), 6.85 (2H, Ph), 6.65 (1H, CH ２ =CH-Ph), 5.63(1H,CH ２ =CH-Ph), 5.14(1H,CH ２ =CH-Ph), 4.51 (2H, PhO-CH ２ -), 3.81 (3H, O-CH ３ ), 1.70 (6H, -CH ３ )

[0147] <Synthesis of Resin MA Using Compound A> [Resin Synthesis Example MA1: Synthesis of Polymer MA1] 4.1 g of Compound A1 obtained in Synthesis Example A1, 1.8 g of 2-ethyl-2-adamantyl methacrylate (EAMA), 0.4 g of γ-butyrolactone methacrylate (GMA), and 1.2 g of 4-vinylphenyl acetate were dissolved in 45 mL of cyclohexanone, and 0.20 g of azobisisobutyronitrile was added. After stirring at an internal temperature of 80°C for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off, rinsed with 20 mL of methanol, and then dried under reduced pressure to obtain 7.6 g of a white powder.

[0148] The obtained white powder was dissolved in 50 mL of tetrahydrofuran. While stirring at 120 rpm using a stirring blade, 40 mL of 1 M aqueous sodium hydroxide solution was gradually added, and the internal temperature was raised to 40 ° C. and stirred for 8 hours. The internal temperature was cooled to 10 ° C., and stirring was continued. 40 mL of 1 M aqueous ammonium chloride solution was gradually added, and stirring was continued for 30 minutes. After that, extraction using 60 mL of ethyl acetate was performed twice, and the obtained organic phase was concentrated by distillation under reduced pressure. 20 mL of ethyl acetate was added to the obtained concentrate, and then 100 mL of hexane was added to cause crystallization. After filtration, the crystal was collected, rinsed with hexane, and vacuum dried to obtain 6.7 g of a white solid, polymer MA1 represented by the following formula (MA1).

[0149] The polymer MA1 had a weight average molecular weight (Mw) of 10,500 and a dispersity (Mw / Mn) of 1.88. １３ As a result of C-NMR measurement, the composition ratio (molar ratio) in the following formula (MA1) was found to be a:b:c:d = 30:30:10:30. Note that, although the following formula (MA1) is written in a simplified form to indicate the ratio of each structural unit, the arrangement order of each structural unit is random, and it is not a block copolymer in which each structural unit forms an independent block.

[0150]

[0151] The composition ratio (molar ratio) of each structural unit in polymer MA1 is １３ C-NMR was measured, and the molar ratio was calculated based on the integral ratio of the carbon at the base of the benzene ring for the polystyrene monomer (Compound A1) and 4-hydroxystyrene (4HSt), and the carbonyl carbon of the ester bond for the methacrylate monomers (2-ethyl-2-adamantyl methacrylate (EAMA) and γ-butyrolactone methacrylate (GMA)).

[0152] [Resin Synthesis Examples MA2 to 10: Synthesis of Polymers MA2 to 10] Each polymer was synthesized in the same manner as in Resin Synthesis Example MA1, except that Compound A1 in Resin Synthesis Example MA1 was replaced with each of the other compounds A.

[0153] Comparative Synthesis Example 1: Synthesis of Comparative Polymer MR1 Comparative polymer MR1 was obtained in the same manner as Resin Synthesis Example MA1, except that compound A1 in Resin Synthesis Example MA1 was replaced with an equimolar amount of 2-ethyl-2-adamantyl methacrylate (EAMA). The molecular weight (Mw) of this resin was 12,300, and the polydispersity (Mw / Mn) was 2.10. In the formula below, "60," "10," and "30" indicate the molar ratio of each structural unit. Although the formula is written in a simplified manner to indicate the ratio of each structural unit, this resin is not a block copolymer in which each structural unit forms an independent block.

[0154]

[0155]

[0156] <Synthesis of Compound BP: Corresponding to the Compound of Formula (2)> [Synthesis Example BP1: Synthesis of Compound BP1] Compound BP1 was synthesized by the method described below.

[0157] A reactor was charged with 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.15 g of methanesulfonic acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 60 mL of DMSO (dimethyl sulfoxide), and stirring was initiated. Subsequently, a Dean-Stark valve and a condenser were used to adjust the reduced pressure conditions to reflux at 120°C, and air was started to be blown into the reaction solution at a flow rate of 1 mL / min. The water collected in the Dean-Stark valve was appropriately discharged outside the system. The reactor was then immersed in a 90°C water bath, and stirring was continued for 30 hours. The reactor was then immersed in a 25°C water bath, and the reaction solution was cooled. The reaction solution was then gradually added to 500 g of a 0.1% by mass aqueous sodium hydrogen sulfite solution with vigorous stirring and mixed. The precipitate was then filtered off using a suction filter, squeezed, and washed with 200 mL of a 33.3% by volume aqueous methanol solution. The obtained precipitate was subjected to column purification to isolate only the main component, and then the solvent was distilled off by evaporation to obtain a solid, which was then dried in vacuum at 40° C. to obtain 8.1 g of a white solid. The yield was 26%.

[0158] As a result of analysis by liquid chromatography-mass spectrometry (LC-MS), it was confirmed that the molecular weight was 743.9, and it was confirmed that the compound BP1 represented by formula (BP1) was obtained. １ H-NMR measurement revealed the following peaks, confirming that the compound had the chemical structure of compound BP1. δ (ppm) (d6-DMSO): 9.6 (2H, OH), 7.5 (2H, Ph), 7.8 (2H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH ３ ), 6.4 to 6.7 (2H, -CH=CH-)

[0159] [Synthesis Examples BP2, BP3, BP6: Synthesis of Compounds BP2, BP3, BP6] Each compound was synthesized in the same manner as in Synthesis Example BP1, except that the raw materials in Synthesis Example BP1 were changed as shown in the table below.

[0160]

[0161]

[0162] <Synthesis of Compound D: Corresponding to the Compound of Formula (3)> [Synthesis Example D2: Synthesis of Compound D2] -Iodination step: Synthesis of DML1D-

[0163] A 100 L stainless steel reaction vessel connected to a reflux condenser was charged with 700 g of 4-hydroxybenzaldehyde and 4900 ml of methanol, and the mixture was dissolved under nitrogen flow and stirred at 220 rpm for 1 hour. The reaction vessel was ice-cooled, and an aqueous sodium hydroxide solution synthesized by dissolving 757 g of sodium hydroxide in 1260 mL of pure water was gradually added to the reaction vessel, followed by the gradual addition of 3200 g of iodine in 10 portions over 60 minutes. The mixture was stirred for 8 hours while maintaining the internal temperature at 60 °C using a water bath. Subsequently, 21 L of a 6 M aqueous hydrochloric acid solution was added dropwise over 1 hour at 120 rpm under ice cooling, followed by 30 minutes of stirring. Next, 2.3 L of a 20% by weight aqueous sodium sulfite solution was added with stirring, followed by 3.5 L of pure water, and the resulting precipitate was collected by filtration. The resulting solid was purified by column chromatography using silica gel to obtain 840 g of DML1D isomer in a yield of 30%.

[0164] -Protective group introduction step: synthesis of protected DML1P-

[0165] Using a 100 L glass-lined reaction vessel equipped with a reflux condenser, 840 g of DML1D was added to 1680 mL of dehydrated dimethylformamide (DMF) in an ice bath under nitrogen flow and stirred with a stirring blade until dissolved. Next, 380 g of diisopropylethylamine was added via a dropping funnel over 30 minutes while stirring in the ice bath, followed by stirring for an additional 60 minutes. 255 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, followed by stirring for an additional 30 minutes in the ice bath. Subsequently, 7.2 L of purified water was added in the ice bath, and after stirring for 60 minutes, the resulting precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in the ice bath for 30 minutes, after which 996 g of the desired protected DML1P was obtained as a white solid by filtration. The yield was 96%.

[0166] - Reduction step: synthesis of compound D2 -

[0167] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 996 g of the synthesized protected product DML1P was gradually added and suspended. Under a nitrogen flow, 19 g of sodium borohydride was added in 3 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 350 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 8 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 2 L of pure water. The resulting precipitate was dissolved in 4 L of ethyl acetate and washed three times with 1.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 80 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystallized product was further rinsed with cold heptane and then dried to obtain 701 g of Compound D2 in a yield of 70% and a purity of 99.2%.

[0168] Synthesis Example D1: Synthesis of Compound D1 Compound D1 was synthesized in the same manner as in Synthesis Example D2, except that salicylaldehyde was used instead of 4-hydroxybenzaldehyde, which was the raw material in Synthesis Example D2.

[0169]

[0170] [Synthesis Example D4: Synthesis of Compound D4]

[0171] A flask equipped with a reflux condenser and a Dean-Stark tube was immersed in an oil bath, and 40 g of 1,3,5-adamantanetriol (Mitsubishi Gas Chemical Company, Inc., 0.22 mol) and 1.3 L of o-xylene were charged into the flask and stirred. Next, 200 g (0.86 mol) of 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was raised to 125°C and the reaction was carried out for 3 hours. This was then stirred for 1 hour in a 25°C water bath. An additional 1.3 L of ion-exchanged water was added to the reaction vessel, and the mixture was separated into an organic phase and an aqueous phase. After recovering the organic phase, it was washed three times with 0.5 L of 5% aqueous sodium bicarbonate solution and then with 0.5 L of ion-exchanged water. After recovering the organic phase, it was concentrated to obtain 17.5 g of a white solid (D4). The product was confirmed by NMR and LC-MS. The molecular weight was 570.

[0172] <Preparation of Raw Material Composition PAY> [Preparation Example PAY1] 50 g of compound A1 was dissolved in 500 g of ethyl acetate. Next, 1000 ppm of compound BP1 was added to compound A1, and the mixture was stirred for 30 minutes. Thereafter, the solvent component was removed by vacuum concentration and vacuum drying to prepare raw material composition PAY1.

[0173] Preparation Examples PAY2 to PAY12 Raw material compositions were prepared in the same manner as in Preparation Example PAY1, except that the types of compounds to be mixed were changed as shown in the table below.

[0174]

[0175] <Synthesis of Resin MAY Using Raw Material Composition PAY> [Resin Synthesis Examples MAY1 to MAY12] Resin MAY was synthesized in the same manner as in Resin Synthesis Example MA, except that raw material composition PAY was used instead of compound A used in Resin Synthesis Example MA described above.

[0176]

[0177] <EB Writing (Evaluation of Sensitivity, Resolution, and Roughness)> - Preparation of Film-Forming Composition - A film-forming composition was prepared by blending 5 parts by mass of the above-mentioned polymer MA or resin MAY, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate (acid generator), 0.1 part by mass of tributylamine, and 94 parts by mass of PGMEA. Furthermore, the prepared film-forming composition was filtered in a clean room using a filter line connected to a PTFE filter (manufactured by Entegris) with a pore size of 15 nm, to obtain a filtered film-forming composition.

[0178] The resulting film-forming composition was applied to a silicon wafer and baked at 110-130°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. The wafer was then exposed to light using an electron beam lithography system (ELS-7500, 100 keV, manufactured by Elionix), baked at 105°C for 60 seconds (PEB), and puddle-developed for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH). The wafer was then rinsed with pure water and rotated at 1500 rpm for 30 seconds to obtain a positive-tone pattern. The resulting pattern was observed using a SEM (S4800, manufactured by Hitachi, Ltd.) to evaluate its sensitivity, resolution, and roughness. The results are shown in the table below.

[0179] Here, the "EB sensitivity" evaluation was carried out based on the lower limit of the exposure dose (mJ / cm) that allows formation of a pattern with a line width of 40 nm and a half pitch of 40 nm. ２ ) was determined as the EB sensitivity.

[0180] For the "resolution" evaluation, a pattern with an L (line) / S (space) ratio of 1 / 1 was used under the pattern layout condition PL, in which the half pitch was reduced by 1 nm from 60 nm, and the exposure dose was 60 mL / cm. ２to 1 mJ / cm ２ Using condition D in which the exposure amount was decreased each time, pattern formability was evaluated using a matrix of conditions PL and D, and the line width at which the resolution was minimized was determined.

[0181] Furthermore, for the "roughness" evaluation, the line width was measured at 30 points at 1 nm intervals per line for any 10 of the obtained line patterns, and the roughness value was evaluated as three times the standard deviation of the line width values.

[0182] <EUV Sensitivity Evaluation> The "EUV sensitivity" of each of the film-forming compositions prepared above was evaluated by the following method: First, each of the prepared film-forming compositions was applied to a separate silicon wafer using a spin coater, and then heat-treated on a hot plate at 105°C for 60 seconds to form a resist layer with a thickness of 100 nm.

[0183] Next, an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by LithoTech Japan Co., Ltd.) was used to expose the film to 1 mJ / cm ２ to 1 mJ / cm ２ 80 mJ / cm ２ After maskless shot exposure with the exposure dose increased to 1000 ppm, the entire wafer was baked (PEB) at 105°C for 60 seconds and puddle developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, yielding a wafer that had undergone 80 shot exposures on the wafer. For each of the resulting shot exposure areas, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness versus exposure dose was obtained, and the exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was determined as the sensitivity value (mJ / cm). ２ ) and used as an index of the EUV sensitivity of the resist. The results are shown in the table below.

[0184] <Evaluation of Plain Film Exposure Defects> The composition used in the EUV exposure sensitivity measurement was applied to a 12-inch silicon wafer having a 100 nm-thick oxide film formed on the outermost surface, and baked at 105°C for 60 seconds to form a 100 nm-thick photoresist layer. Next, using an extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, manufactured by Litho Tech Japan Co., Ltd.), the entire wafer was subjected to shot exposure at the same exposure dose as the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, and the wafer was further baked at 105°C for 90 seconds (PEB) and paddle developed for 60 seconds with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution, yielding an exposed wafer in which the entire wafer had been subjected to 80 shots of shot exposure.

[0185] The exposed wafer was then subjected to etching using a Telius SCCM etching system (product name, manufactured by Tokyo Electron Ltd.). ４ / CF ４ Etching was performed using Ar / Ar gas until the oxide film thickness reached 40 nm. The wafers produced by etching were subjected to defect evaluation using a defect inspection device "Surfscan SP3" (product name, manufactured by KLA Corporation), and the number of cone defects of 25 nm or more was calculated as an index of etching defects according to the following evaluation criteria. The results are shown in the table below.

[0186] (Evaluation criteria) S: Number of cone defects ≦ 5 A: 5 < Number of cone defects ≦ 20 B: 20 ​​< Number of cone defects ≦ 60 C: 60 < Number of cone defects ≦ 400 D: 400 < Number of cone defects

[0187]

[0188]

[0189] From the above results, it was found that the film-forming compositions of the examples were capable of forming films that were excellent in sensitivity, resolution, roughness, EUV sensitivity, and solid film exposure defects.

Claims

1. A composition comprising a compound represented by the following formula (1) and / or a (co)polymer containing a structural unit derived from the compound represented by the formula (1), and at least one compound selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (X): [In formula (1), A represents an aromatic group which may have a substituent (excluding halogen atoms) or a cyclic aliphatic group which may have a substituent (excluding halogen atoms), B represents an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent, Q represents a dissociable group, and R ０ represents a group having an unsaturated double bond, each X is independently a halogen atom, and n is an integer of 1 to 6. [In formula (2), each C1 independently represents an aromatic group which may have a substituent, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n １１ are each independently an integer of 0 to 6, and k is an integer of 0 to 6. [In formula (3), each C2 independently represents an aliphatic group which may have a substituent or an aromatic group which may have a substituent, I represents an iodine atom, and n ２２ are each independently an integer of 0 to 6, ２ are each independently a single bond or a divalent linking group, and m is an integer of 0 to 6. [In formula (X), each C1 is independently an aromatic group which may have a substituent, each C3 is independently an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and Q １ are each independently a dissociable group, and R ａ are each independently a hydrogen atom, a methyl group, or a halogen atom; ｂ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; ｃ are each independently a hydrogen atom, an aliphatic group, or a halogen atom; １ are each independently a single bond or a divalent linking group, I is an iodine atom, and n ３３ are each independently an integer of 0 to 6, and k is an integer of 0 to 6.

2. The compound represented by formula (1) is a compound represented by formula (1-1): [In formula (1-1), B, Q, X, and n are as defined above, and R ｘ ~R ｚ are each independently a hydrogen atom, an aliphatic group, or a halogen atom, or R ｘ and R ｙ , or R ｙ and R ｚ may form a cyclic structure together with the carbon atoms to which they are attached, R 1 are each independently an alkoxy group or a linear, branched or cyclic monovalent group having 1 to 30 carbon atoms and not containing a polymerizable unsaturated bond, １ is an integer of 0 to 4. The composition according to claim 1 .

3. The compound represented by the formula (1-1) is a compound represented by the following formula (1-2): [In formula (1-2), B, Q, X, n, R ｘ ~R ｚ , R 1 and n １ is as described above, and R ２ are each independently an alkoxy group, —OR ２Ａ OR ２Ｂ , or —OC(═O)—R ２Ｃ and R ２Ａ is an alkylene group, R ２Ｂ is an alkyl group, and R ２Ｃ is an alkoxy group, and n ２ The composition according to claim 2, wherein n is an integer of 1 to 4.

4. The composition according to claim 1, wherein Q in formula (1) contains a carbonate group, an acetal group, an ether group, or an alkyloxy group.

5. Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ The composition according to claim 1, wherein each independently represents an alkylene group optionally substituted with an alkyl group, and an asterisk * represents a linking moiety.

6. Q in the formula (1) has a structure selected from the following formulas: The composition of claim 1, wherein the asterisk * indicates a linking moiety.

7. The composition according to claim 1, wherein B in said formula (1) is a benzene ring which may have a substituent, or an adamantane ring which may have a substituent.

8. The composition according to claim 1, wherein X in formula (1) is an iodine atom.

9. The composition according to claim 1, wherein at least one C1 in said formula (2) is a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent.

10. The composition according to claim 1, wherein at least one C2 in the formula (3) is an aromatic group which may have a substituent, or a cyclic aliphatic group which may have a substituent.

11. The composition according to claim 1, wherein at least one C1 in formula (X) is a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent.

12. The composition according to claim 1, wherein the total amount of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (X) relative to the total amount of the composition is 1 ppm to 100,000 ppm.

13. The composition according to claim 1 for forming a film.

14. The composition according to claim 1 for forming a film for semiconductor lithography.

15. The composition according to claim 1, for forming a resist film for semiconductor lithography.

16. A compound represented by the following formula (1): [In formula (1), A represents an aromatic group which may have a substituent (excluding halogen atoms) or a cyclic aliphatic group which may have a substituent (excluding halogen atoms), B represents an aromatic group which may have a substituent or a cyclic aliphatic group which may have a substituent, Q represents a dissociable group, and R ０ represents a group having an unsaturated double bond; each X is independently a halogen atom; and n is an integer of 1 to 6.

17. The compound represented by formula (1) is represented by the following formula (1-1): [In formula (1-1), B, Q, X, and n are as defined above, and R ｘ ~R ｚ are each independently a hydrogen atom, an aliphatic group, or a halogen atom, or R ｘ and R ｙ , or R ｙ and R ｚ may form a cyclic structure together with the carbon atoms to which they are attached, R 1 are each independently an alkoxy group or a linear, branched or cyclic monovalent group having 1 to 30 carbon atoms and not containing a polymerizable unsaturated bond, １ is an integer of 0 to 4. The compound according to claim 16.

18. The compound represented by formula (1-1) is represented by formula (1-2): [In formula (1-2), B, Q, X, n, R ｘ ~R ｚ , R 1 and n １ is as described above, and R ２ are each independently an alkoxy group, —OR ２Ａ OR ２Ｂ , or —OC(═O)—R ２Ｃ and R ２Ａ is an alkylene group, R ２Ｂ is an alkyl group, and R ２Ｃ is an alkoxy group, and n ２ is an integer of 1 to 4. The compound according to claim 17.

19. The compound according to claim 16, wherein Q in formula (1) contains a carbonate group, an acetal group, an ether group, or an alkyloxy group.

20. Q in the formula (1) has a structure selected from the following formulas: [In the formula, R Ｑ１ ~R Ｑ６ each independently represents an alkylene group optionally substituted with an alkyl group, and an asterisk * represents a linking moiety.

21. Q in the formula (1) has a structure selected from the following formulas: The compound of claim 16, wherein the asterisk * indicates a linking moiety.

22. The compound according to claim 16, wherein B in the formula (1) is an optionally substituted benzene ring or an optionally substituted adamantane ring.

23. The compound according to claim 16, wherein X in formula (1) is an iodine atom.

24. A (co)polymer containing a structural unit derived from the compound according to claim 16.

25. A composition comprising the compound of claim 16 and / or the (co)polymer of claim 24.

26. The composition according to claim 25 for forming a film.

27. The composition of claim 25 for forming a film for semiconductor lithography.

28. The composition according to claim 25, for forming a resist film for semiconductor lithography.

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