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

Abstract

A compound represented by formula (1). (In formula (1), A1 represents an optionally substituted aromatic group, I represents an iodine atom, Q independently represents a dissociative group, A2 independently represents an optionally substituted aliphatic group or aromatic group, Ra independently represents a hydrogen atom, a methyl group, or a halogen atom, Rb and Rc independently represent a hydrogen atom, an aliphatic group, or a halogen atom, and X represents a hydrogen atom, a methyl group, or a halogen atom. Each X1 independently represents a single bond or a divalent linking group, p represents an integer of 1-2, n1 represents an integer of 1-6, n2 represents an integer of 1-6, and z represents an integer of 1 or more. )

Description

Technical Field

[0001] This invention relates to compounds, compositions, resin compositions, compositions for film formation, compositions for photolithography, and compositions for resist film formation. Background Technology

[0002] In recent years, with the advancement of photolithography technology, the miniaturization of semiconductors (patterns) and pixels has rapidly progressed in the manufacturing of semiconductor components and liquid crystal display components. As a method for pixel miniaturization, the wavelength of the exposure light source is generally shortened. Specifically, ultraviolet light, represented by gamma rays and i-rays, was previously used, but now far-ultraviolet exposure, such as KrF excimer lasers (248nm) and ArF excimer lasers (193nm), has become the focus of mass production, and the introduction of extreme ultraviolet (EUV) lithography (13.5nm) is continuously developing. In addition, electron beams (EB) are also used to form fine patterns.

[0003] To date, common photoresist materials are polymeric photoresist materials capable of forming amorphous films. Examples include polymethyl methacrylate, polyhydroxystyrene with acid-dissociable groups, or alkyl polymethyl methacrylate (see, for example, Non-Patent Literature 1 below).

[0004] Existing technical documents

[0005] Non-patent literature

[0006] Non-Patent Document 1: Nobuji Okazaki and 8 others, "40 Years of Photolithography," S&T published, December 9, 2016. Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, there is still room for improvement in the sensitivity, resolution, and roughness of resins and other materials that use photoresist, and there is a need to improve the sensitivity to EUV and improve the exposure defects that occur when forming solid films.

[0009] In view of the above, the object of the present invention is to provide compounds that can form films with excellent sensitivity, resolution, roughness and EUV sensitivity, as well as compositions using the same, resin compositions, film forming compositions and film forming compositions for photolithography.

[0010] Solution for solving the problem

[0011] <1>

[0012] A compound represented by the following formula (1).

[0013]

[0014] (In formula (1),)

[0015] A1 represents an aromatic group with optional substituents.

[0016] I represents an iodine atom.

[0017] Q represents a dissociative group independently.

[0018] A2 independently represents either an aliphatic or aromatic group with substituents.

[0019] R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom.

[0020] R b and R c Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom.

[0021] X 1 Each can independently represent a single bond or a divalent linker.

[0022] p represents an integer from 1 to 2.

[0023] n 1 Represents integers from 1 to 6.

[0024] n 2 Represents integers from 1 to 6.

[0025] z represents an integer greater than or equal to 1.

[0026] <1A>

[0027] A compound represented by the following formula (1A).

[0028]

[0029] (In formula (1A),

[0030] A1 represents an aromatic group with optional substituents.

[0031] I represents an iodine atom.

[0032] Q represents a dissociative group.

[0033] A2 represents an optional aliphatic or aromatic group with substituents.

[0034] R a Indicates a hydrogen atom, methyl group, or halogen atom.

[0035] R b and Rc Represents a hydrogen atom, an aliphatic group, or a halogen atom.

[0036] X 1 Indicates a single bond or a divalent linker.

[0037] p represents an integer from 1 to 2.

[0038] n 1 Represents integers from 1 to 6.

[0039] n 2 (Represents integers from 1 to 6.)

[0040] <2>

[0041] according to <1> Or the compound described in <1A>, wherein A1 is optionally a benzene ring or a naphthalene ring having substituents.

[0042] <3>

[0043] according to <1> <1A>~ <2> The compound of any one of the following, wherein A2 is optionally an aromatic group having a substituent or a cyclic aliphatic group.

[0044] <4>

[0045] according to <1> <1A>~ <3> The compound in any one of the following statements, wherein the dissociative group is a carbonate group, an acetal group, an ether group, or an alkoxy group.

[0046] <5>

[0047] according to <1> <1A>~ <4> The compound in any one of the following statements, wherein n 1 It is 1~2.

[0048] <6>

[0049] according to <1> <1A>~ <5> The compound in any one of the following statements, wherein n 2 It is 1~2.

[0050] <7>

[0051] according to <1> <1A>~ <6> The compound described in any one of the following statements, wherein z is 1 to 2.

[0052] <8>

[0053] A composition comprising: <1> <1A>~ <7> The compound of any one of the following, and at least one compound selected from the compound shown in formula (2), the compound shown in formula (3) and the compound shown in formula (X).

[0054]

[0055] (In equation (2), A1, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, R... a R b R c X 1 n 11 (Choose any two that are the same or different)

[0056] k represents an integer from 0 to 6.

[0057]

[0058] In equation (3), A2 and I have the same meaning as in equation (1), and n 22 Represents integers from 0 to 6 (where multiple A2, n) 22 X 2 (Choose any two that are the same or different)

[0059] X 2 Indicates a single bond or a divalent linker.

[0060] m represents an integer from 0 to 6.

[0061]

[0062] (In formula (X), A1, A2, Q, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, A2, Q, R) a R b R c X 1 n 11 (Choose any two that are the same or different)

[0063] k represents an integer from 0 to 6.

[0064] <9>

[0065] according to <8> The composition wherein at least one A1 in formula (2) is optionally a benzene ring or a naphthalene ring having a substituent.

[0066] <10>

[0067] according to <8> or <9> The composition wherein at least one A2 in formula (3) is optionally an aromatic group or a cyclic aliphatic group having a substituent.

[0068] <11>

[0069] according to <8> ~ <10> The composition of any one of the following, wherein at least one A1 in the formula (X) is optionally a benzene ring or a naphthalene ring having a substituent.

[0070] <12>

[0071] according to <8> ~ <11> The composition according to any one of the following, wherein the total amount of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (X) is 1 ppm by mass to 100,000 ppm by mass relative to the total amount of the composition.

[0072] <13>

[0073] A (co)polymer comprising with <1> <1A>~ <7> The structural unit corresponding to the compound mentioned in any one of the above.

[0074] <14>

[0075] A resin composition comprising: <13> The (co)polymer, and at least one compound selected from the compounds shown in formula (2), formula (3), and formula (X).

[0076]

[0077] (In equation (2), A1, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, R... a R b R c X 1 n 11 (Choose any two that are the same or different)

[0078] k represents an integer from 0 to 6.

[0079]

[0080] In equation (3), A2 and I have the same meaning as in equation (1), and n 22 Represents integers from 0 to 6 (where multiple A2, n) 22 X 2(Choose any two that are the same or different)

[0081] X 2 Indicates a single bond or a divalent linker.

[0082] m represents an integer from 0 to 6.

[0083]

[0084] (In formula (X), A1, A2, Q, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, A2, Q, R) a R b R c X 1 n 11 (Choose any two that are the same or different)

[0085] k represents an integer from 0 to 6.

[0086] <15>

[0087] A film-forming composition comprising <1> <1A>~ <7> any one of the compounds, <8> ~ <12> The composition described in any one of the following statements, <13> The (co)polymer or <14> The resin composition described above.

[0088] <16>

[0089] according to <15> The film-forming composition is a film-forming composition for semiconductor photolithography.

[0090] <17>

[0091] according to <15> The film-forming composition is a resist film-forming composition for semiconductor photolithography.

[0092] <18>

[0093] A compound represented by the following formula (X).

[0094]

[0095] (in formula (X),

[0096] A1 represents an aromatic group with optional substituents.

[0097] I represents an iodine atom.

[0098] Q represents a dissociative group.

[0099] A2 represents an optional aliphatic or aromatic group with substituents.

[0100] R a Indicates a hydrogen atom, methyl group, or halogen atom.

[0101] R b and R c Represents a hydrogen atom, an aliphatic group, or a halogen atom.

[0102] X 1 Indicates a single bond or a divalent linker.

[0103] n 11 Represents integers from 0 to 6 (where multiple A1, A2, Q, R) a R b R c X 1 n 11 (Choose any two that are the same or different)

[0104] k represents an integer from 0 to 6.

[0105] <19>

[0106] A compound represented by the following formula (W).

[0107]

[0108] (in formula (W),

[0109] A1 represents an aromatic group with optional substituents.

[0110] I represents an iodine atom.

[0111] R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom.

[0112] R b and R c Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom.

[0113] X 1 Each independently represents a divalent linker.

[0114] p represents an integer from 1 to 2.

[0115] n 1 Represents integers from 1 to 6.

[0116] z represents an integer greater than or equal to 1.

[0117] <20>

[0118] according to <19> The compound, wherein, in formula (W), X 1 The divalent linker shown is -R 3 -O-,R 3 This indicates an alkenyl group that may have a substituent.

[0119] The effects of the invention

[0120] According to the present invention, compounds capable of forming films with excellent sensitivity, resolution, roughness and EUV sensitivity, as well as compositions using the same, resin compositions, film-forming compositions and film-forming compositions for photolithography, are provided. Detailed Implementation

[0121] Hereinafter, embodiments of the present invention will be described (hereinafter sometimes referred to as "this embodiment"). It should be noted that this embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0122] In this specification, (meth)acrylate refers to acrylates and methacrylates. Other terms containing the expression (methyl) are interpreted in the same way as (meth)acrylate.

[0123] In this specification, (co)polymers refer to homopolymers and copolymers.

[0124] In this specification, “X~Y” includes X and Y as its endpoints.

[0125] Compound A

[0126] The compound of this embodiment is represented by the following formula (1). Hereinafter, the compound shown in formula (1) will be appropriately referred to as "compound A". Compound A can be used to synthesize the (co)polymer of this embodiment, which will be described later.

[0127]

[0128] (In formula (1),)

[0129] A1 represents an aromatic group with optional substituents.

[0130] I represents an iodine atom.

[0131] Q represents a dissociative group independently.

[0132] A2 independently represents either an aliphatic or aromatic group with substituents.

[0133] R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom.

[0134] R b and Rc Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom.

[0135] X 1 Each can independently represent a single bond or a divalent linker.

[0136] p represents an integer from 1 to 2.

[0137] n 1 Represents integers from 1 to 6.

[0138] n 2 Represents integers from 1 to 6.

[0139] z represents an integer greater than or equal to 1.

[0140] In addition, as one of the preferred methods of the above formula (1), the following can be cited.

[0141]

[0142] (In formula (1A),

[0143] A1 represents an aromatic group with optional substituents.

[0144] I represents an iodine atom.

[0145] Q represents a dissociative group.

[0146] A2 represents an optional aliphatic or aromatic group with substituents.

[0147] R a Indicates a hydrogen atom, methyl group, or halogen atom.

[0148] R b and R c Represents a hydrogen atom, an aliphatic group, or a halogen atom.

[0149] X 1 Indicates a single bond or a divalent linker.

[0150] p represents an integer from 1 to 2.

[0151] n 1 Represents integers from 1 to 6.

[0152] n 2 (Represents integers from 1 to 6.)

[0153] Compound A has a structure in which a site centered on A1 (hereinafter sometimes referred to as "A1 part") and a site centered on A2 (hereinafter sometimes referred to as "A2 part") are linked by a dissociable group Q. Iodine atoms are bonded to both A1 and A2 parts. The (co)polymer formed by resinifying compound A exhibits high absorption capacity for exposure light when used as a film-forming composition due to the presence of iodine atoms, and can efficiently generate secondary electrons during exposure. Therefore, the film-forming composition becomes highly sensitive, improving the acid-generating efficiency of the exposure section based on the acid-generating agent. Furthermore, compound A exhibits high resistance to developer solubility before the A1 and A2 parts decompose due to the influence of iodine atoms, etc. On the other hand, after the A1 and A2 parts decompose due to acids generated during exposure, the resistance to developer solubility decreases significantly. In other words, the A2 part of compound A functions as a protective group for the developer; therefore, when a polymer with structural units corresponding to compound A is manufactured, the contrast between solubility before and after exposure can be improved.

[0154] Thus, the film-forming composition using a polymer having structural units corresponding to compound A can exhibit high sensitivity and high solubility contrast, thereby improving the sensitivity, resolution, roughness, and EUV sensitivity of the formed film, and further suppressing the generation of exposure defects during the formation of a solid film.

[0155] The following is a description of compound A.

[0156] In the above formula (1) (preferred formula (1A)), A1 represents an aromatic group optionally having a substituent. Preferably, this aromatic group has 4 to 60 carbon atoms, and more preferably, it has 6 to 30 carbon atoms. In formula (1) (preferred formula (1A)), A1 is preferably a benzene ring or naphthalene ring optionally having a substituent, and more preferably a benzene ring, considering its polymerizability when copolymerized using the compound of formula (1) (preferably the compound of formula (1A)) and the improved sensitivity, resolution, roughness, and other properties when applied to photolithography after polymerization. It should be noted that, as shown in formulas (1) and (1A), A1 is bonded with an iodine atom; therefore, the substituent optionally present in A1 is different from that of iodine.

[0157] In this embodiment, unless otherwise defined, "substitution" refers to the substitution of one or more hydrogen atoms in a functional group by a substituent. There are no particular limitations on the term "substituent," and examples include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, thiols, heterocyclic groups, alkyl groups with 1 to 30 carbon atoms, aryl groups with 6 to 30 carbon atoms, alkoxy groups with 1 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, alkynyl groups with 2 to 30 carbon atoms, acyl groups with 1 to 30 carbon atoms, and amino groups with 0 to 30 carbon atoms.

[0158] Alkyl groups can be any of the following: straight-chain aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups.

[0159] Examples of alkyl groups having 1 to 30 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-dodecyl, valeryl, etc.

[0160] Examples of aryl groups with 6 to 30 carbon atoms include, but are not limited to, phenyl, naphthyl, biphenyl, anthracene, pyrene, and perylene.

[0161] Examples of alkenyl groups with 2 to 30 carbon atoms include, but are not limited to, ethynyl, propenyl, butynyl, and pentyynyl.

[0162] Examples of alkynyl groups with 2 to 30 carbon atoms include, but are not limited to, acetylenyl and ethynyl.

[0163] Examples of alkoxy groups with 1 to 30 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and pentoxy.

[0164] The substituents present in A1 are not particularly limited. Examples include halogen atoms (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiols, heterocyclic groups, straight-chain aliphatic hydrocarbon groups, branched-chain aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkanoyloxy groups, aramidoxy groups, alkylsilyl groups, etc. Preferably, alkoxy groups containing an ether bond, such as methoxy, ethoxy, and ethoxyethyloxy, are examples. It should be noted that, as shown in formulas (1) and (1A), A1 is bonded with an iodine atom; therefore, the substituents optionally present in A1 are different from those of iodine.

[0165] In formula (1) above (preferred formula (1A)), Q represents a dissociative group. Here, "dissociative group" refers to a group that, upon cleavage in the presence of an acid or base, produces a base-soluble group (e.g., phenolic hydroxyl, carboxyl, sulfonic acid, hexafluoroisopropanol). As for Q in compound A, it is preferably an acid-dissociative group that dissociates through an acid. There are no particular limitations on the acid-dissociative group; for example, it can be appropriately selected from groups derived from hydroxyl styrene resins, (meth)acrylic resins, etc., used in chemically amplified resist compositions for KrF and ArF. Specific examples of acid-dissociative groups include those described in International Publication No. 2016 / 158168. More specifically, as Q, considering the efficiency based on acid dissociation, particularly the efficiency of deprotection reactions based on acid dissociation behavior near 100°C, and stability over time, groups having oxygen atoms such as carbonate, acetal, ether, or alkoxy groups can be cited. Specifically, divalent groups such as the following (where...) can be cited. (Indicates the connecting part).

[0166]

[0167] In the formula representing the divalent group, R z Represents a group with two or more carbon atoms. R z It can be with A 2 Or A 2 The substituents on it form a ring structure. As R... z The groups shown with 2 or more carbon atoms can be cyclic structures with 2 to 20 carbon atoms, such as aromatic groups with 6 to 20 carbon atoms and cyclic aliphatic groups with 3 to 20 carbon atoms.

[0168] In equation (1) (preferred equation (1A)), R a This represents a hydrogen atom, a methyl group, or a halogen atom. Additionally, in formula (1) (preferred formula (1A)), R... b and R c This represents a hydrogen atom, an aliphatic group, or a halogen atom. For halogen atoms, F, Cl, Br, I, etc., can be used appropriately. Additionally, R... b and R c The aliphatic group is not particularly limited; examples include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. a R b and R c The combination of atoms is not particularly limited, but it is preferred that any of them be hydrogen atoms or methyl groups, and even more preferably all of them be hydrogen atoms.

[0169] In equation (1) (preferred equation (1A)), X 1This indicates a single bond or a divalent linking group. There are no particular limitations on the divalent linking group; it can be a group that does not dissociate from acids or bases. Examples of divalent linking groups include ether bonds, divalent aliphatic groups, ester groups, carbonyl groups, amide groups, imide groups, carbamate groups, urea groups, alkylene oxides, oxoalkylene oxides, and groups further substituented thereon. X can be... 1 The divalent linking group shown is alkyleneoxy, and more specifically, it can be -R. 3 -O-〔R 3 [: indicates an alkenyl group with optional substituents]. As R 3 The alkenyl group shown is preferably an alkenyl group with 1 to 3 carbon atoms in terms of stability, and more preferably an alkenyl group with 1 to 2 carbon atoms. As such a "-R" 3 -O-” and R a R b and R c Specific examples of combinations of these can be given, for example, as follows (in the following, " "Indicates the bonding portion with A1".

[0170]

[0171] In formula (1) (preferred formula (1A)), A2 represents an aliphatic or aromatic group optionally having a substituent. From the perspective of improving sensitivity, resolution, roughness, and other performance aspects when applied to photolithography processes, an aromatic group optionally having a substituent or a cyclic aliphatic group is preferred, and a benzene ring or adamantane optionally having a substituent is even more preferred. Examples of aliphatic groups include those with 1 to 30 carbon atoms. Examples of such aliphatic groups include aliphatic groups having a non-alicyclic skeleton, aliphatic groups having an alicyclic skeleton, and combinations thereof.

[0172] There are no particular limitations on the aliphatic group having a non-alicyclic skeleton. Examples include alkanes with 1 to 30, 1 to 20, 1 to 10, or 1 to 6 carbon atoms that may have substituents; alkenes with 2 to 30, 2 to 20, 2 to 10, or 2 to 6 carbon atoms that may have substituents; alkynes with 2 to 30, 2 to 20, 2 to 10, or 2 to 6 carbon atoms that may have substituents; and combinations thereof.

[0173] Furthermore, there are no particular limitations on the alicyclic skeleton of the aliphatic group. Examples include cycloalkanes with 3 to 30, 3 to 20, 3 to 10, or 3 to 6 carbon atoms that may have substituents; cycloalkenes with 3 to 30, 3 to 20, 3 to 10, or 3 to 6 carbon atoms that may have substituents; cycloalkynes with 3 to 30, 3 to 20, 3 to 10, or 3 to 6 carbon atoms that may have substituents; and combinations thereof.

[0174] From the viewpoint of reducing deprotection energy, improving resolution, and reducing defects during pattern formation, A2 is preferably a cyclic aliphatic group, more preferably having a polycyclic alicyclic skeleton, and even more preferably having an adamantane skeleton. In particular, the adamantane cation has very high stability, which is believed to significantly reduce the deprotection energy.

[0175] As shown in A2, the aromatic group is the same as in the example of A1 above.

[0176] There are no particular limitations on the specific examples of compounds that can form the skeleton of A2. Examples include, by choice, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, eicosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloeicosane, cyclotriacontane, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, eicosene, triacontane, benzene, naphthalene, and combinations thereof. These can contain ether bonds, ketone bonds, or ester bonds.

[0177] The substituents that A2 may have are not particularly limited. Examples include halogen atoms (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiols, heterocyclic groups, straight-chain aliphatic hydrocarbon groups, branched-chain aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkanoyloxy groups, arylsilyl groups, and alkoxy groups, optionally including ether bonds such as hydroxyl, methoxy, ethoxy, and ethoxyethyloxy. It should be noted that, as shown in formulas (1) and (1A), an iodine atom is bonded to A2, therefore the substituents that A2 may have are different from those of iodine.

[0178] In formula (1) (preferred formula (1A)), I represents an iodine atom. 1 The number of I atoms on A1 is an integer from 1 to 6. From the perspective of sensitizing effect, solubility in solvents, and chemical stability, n... 1 Preferably, it is an integer from 1 to 3, and more preferably, it is an integer from 1 to 2.

[0179] Similarly, n 2The number of I atoms on A2 is an integer from 1 to 6. From the perspective of sensitizing effect, solubility in solvents, and chemical stability, n... 2 Preferably, it is an integer from 1 to 3, and more preferably, it is an integer from 1 to 2.

[0180] z represents “Q-A2-(I)n” on A1. 2 The number of "z" is an integer greater than or equal to 1. From the point of view of stability, z is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0181] Regarding the total number of iodine atoms in compound A, it is preferably 2 to 5 in terms of improving the sensitivity of G and the stability of the compound, and more preferably 2 or 3.

[0182] (Specific examples of compound A)

[0183] The following are specific examples of compound A, but the present invention is not limited to this compound.

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218] Compound A can be manufactured by the methods described in the examples below. Furthermore, the compound A obtained by the reaction can be purified to the desired high purity monomer using known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or combinations thereof.

[0219] (Compound (W))

[0220] As a raw material for manufacturing compound A, for example, a compound represented by the following formula (W) can be used.

[0221]

[0222] (in formula (W),

[0223] A1 represents an aromatic group with optional substituents.

[0224] I represents an iodine atom.

[0225] R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom.

[0226] R b and R c Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom.

[0227] X 1 Each independently represents a divalent linker.

[0228] p represents an integer from 1 to 2.

[0229] n 1 Represents integers from 1 to 6.

[0230] z represents an integer greater than or equal to 1.

[0231] In formula (W), A1, I, and R a R b and R c X 1 p, n 1 The meanings of and z are the same as in equation (1) above. It should be noted that in equation (W), X can be... 1 The divalent linking group shown is alkyleneoxy, and more specifically, it can be -R. 3 -O-〔R 3 [: indicates an alkenyl group with optional substituents]. As R 3 The alkenyl group shown is preferably an alkenyl group with 1 to 3 carbon atoms in terms of stability, and more preferably an alkenyl group with 1 to 2 carbon atoms. Such a "-R" 3 -O-” and R a R b and R c Combinations of these can be exemplified as follows (in the following, " "Indicates the bonding portion with A1".

[0232]

[0233] Furthermore, in formula (W), considering that Z is an integer greater than or equal to 1, Z is preferably 1 to 3, and more preferably 1 or 2. Although not particularly limited, the following compounds can be cited as compounds represented by formula (W).

[0234]

[0235] The compound represented by formula (W) can be manufactured by converting the alcohol having the corresponding structure into a vinyl ether, as described in the examples below. Furthermore, the compound represented by formula (W) obtained by the reaction can be purified to the desired high purity monomer using known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or combinations thereof.

[0236] Raw Material Composition

[0237] The composition of this embodiment (hereinafter, sometimes referred to as the "starter composition") is a composition comprising compound A as described above, and at least one compound selected from the compounds shown in formula (2), formula (3), and formula (X) below (hereinafter, the compounds shown in formula (2), formula (3), and formula (X) are collectively referred to as "compound B"). The starter composition can be used to synthesize the (co)polymer of this embodiment described later.

[0238] Specifically, the (co)polymer of this embodiment can be synthesized by polymerizing the raw material composition and monomers corresponding to other structural units described later. Additionally, the raw material composition may also contain additives such as solvents and polymerization initiators that can be used in the manufacturing method of the (co)polymer described later.

[0239] <Compound B>

[0240] Compound B is broadly classified into the compound shown in formula (2) (hereinafter sometimes referred to as "compound B2"), the compound shown in formula (3) (hereinafter sometimes referred to as "compound B3") and the compound shown in formula (X) (hereinafter sometimes referred to as "compound BX").

[0241] (Compound B2: The compound shown in formula (2))

[0242] Compound B2 is the compound shown in formula (2).

[0243]

[0244] (In equation (2), A1, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, R... a R b R c X 1 n 11 (Choose any two numbers that are the same or different), where k represents an integer from 0 to 6.

[0245] In equation (2), A1 and R a R b R c X 1 The meanings of A1 and I in equation (1) are the same, and the specific examples are also the same. It should be noted that multiple A1 and R... a R b R c n 11 X 1 Choose either the same or different.

[0246] Specifically, in terms of affinity or compatibility with compounds of formula (1) (preferably compounds of formula (1A)), at least one A1 in formula (2) is preferably a benzene ring or naphthalene ring optionally having a substituent, more preferably a benzene ring having at least any of hydroxyl and methoxy groups, and particularly preferably a benzene ring having both hydroxyl and methoxy groups.

[0247] In equation (2), k represents an integer from 0 to 6. Considering both the effect on stability over time and the lithographic performance such as sensitivity, resolution, and roughness of compound B2, k is preferably 0 or 1, and more preferably 0.

[0248] In the formula, each R a R b and R c The combination is not particularly limited, but it is preferred that any of them be hydrogen or methyl, and even more preferably all of them be hydrogen atoms.

[0249] In equation (2), n 11 Represents integers from 0 to 6. n in compound B2 11 Preferably, the number is 1 to 6, more preferably 1 or 2. Regarding the total number of iodine atoms in compound B2 as a whole, it is preferably 1 to 5 in terms of affinity or compatibility with compounds of formula (1) (preferably compounds of formula (1A)) and effect on stability over time, and more preferably 2 to 4.

[0250] Compound B2 can be prepared by the methods described in the examples below. Alternatively, the compound B2 obtained by the reaction can be purified to the desired high purity monomer by well-known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or combinations thereof.

[0251] (Specific examples of compound B2)

[0252] The following shows specific examples of compound B2. However, compound B2 is not limited to the following compounds.

[0253]

[0254] (Compound B3: the compound shown in formula (3))

[0255] Compound B3 is the compound shown in formula (3).

[0256]

[0257] In equation (3), A2 and I have the same meaning as in equation (1), and n 22 Represents integers from 0 to 6 (where multiple A2, n) 22 X 2 Choose any two that are the same or different), X 2 (This indicates a single bond or a divalent linker, where m represents an integer from 0 to 6.)

[0258] In equation (3), A2 and I have the same meaning as in equation (1), and the specific examples are also the same. It should be noted that multiple A2 and n... 22 X 2 Choose either the same or different.

[0259] Specifically, in terms of compatibility or affinity with compounds of formula (1) (preferably compounds of formula (1A)), at least one A2 in formula (3) is preferably an aromatic group or a cyclic aliphatic group optionally having a substituent, more preferably a benzene ring or adamantane optionally having a substituent, and particularly preferably a benzene ring or adamantane having at least one selected from hydroxyl, alkoxy with 1 to 3 carbon atoms optionally having an ether bond, and alkyl with 1 to 2 carbon atoms optionally having a hydroxyl group.

[0260] In equation (3), m represents an integer from 0 to 6. Considering both the effect on stability over time and the lithographic performance such as sensitivity, resolution, and roughness of compound B3, m is preferably 0 or 1, and more preferably 0.

[0261] In equation (3), n 22 Represents integers from 0 to 6. n in compound B3 22 Preferably, it is 1 to 6, more preferably 0 or 1. Regarding the total number of iodine atoms in compound B3 as a whole, it is preferably 0 to 3 in terms of affinity or compatibility with compounds of formula (1) (preferably compounds of formula (1A)) and effect on stability over time, and more preferably 1 or 2.

[0262] In equation (3), X 2 This indicates a single bond or a divalent linker. Examples of divalent linkers include those related to X mentioned above. 1 A similar specific example. X in compound B3. 2 Preferably, it is either a single bond or an ether bond.

[0263] Compound B3 can be prepared by the methods described in the examples below. Alternatively, compound B2 obtained by the reaction can be purified to the desired high purity monomer by well-known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or combinations thereof.

[0264] (Specific examples of compound B3)

[0265] The following shows specific examples of compound B3. However, compound B3 is not limited to the following compounds.

[0266]

[0267] (Compound BX: The compound represented by formula (X))

[0268] Compound BX is the compound represented by the following formula (X).

[0269]

[0270] (In formula (X), A1, A2, Q, R) a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6 (where multiple A1, A2, Q, R) a R b R c X 1 n 11 (Choose any two numbers that are the same or different), where k represents an integer from 0 to 6.

[0271] In equation (X), A1, A2, Q, and R... a R b R c X 1 The meanings of A1, A2, Q, and R are the same as in equation (1), and the specific examples are also the same. It should be noted that multiple A1, A2, Q, and R... a R b R c n 11 X 1 Choose either the same or different.

[0272] Specifically, in terms of affinity or compatibility with compounds of formula (1) (preferably compounds of formula (1A)), at least one A1 in formula (X) is preferably a benzene ring or naphthalene ring optionally having a substituent, more preferably a benzene ring having at least any of hydroxyl and methoxy groups, and particularly preferably a benzene ring having both hydroxyl and methoxy groups.

[0273] In formula (X), k represents an integer from 0 to 6. Considering both the effect on stability over time and the lithographic performance such as sensitivity, resolution, and roughness in compound BX, k is preferably 0 or 1, and more preferably 0.

[0274] In the formula, each R a R b and R c The combination is not particularly limited, but it is preferred that any of them be hydrogen or methyl, and even more preferably all of them be hydrogen atoms.

[0275] In equation (X), n 11 n represents an integer from 0 to 6. In compound BX, n... 11 Preferably, the number is 1 to 6, more preferably 1 or 2. Regarding the total number of iodine atoms in the compound BX as a whole, it is preferably 1 to 5 in terms of affinity or compatibility with the compound of formula (1) (preferably the compound of formula (1A)) and effect on stability over time, and more preferably 2 to 4.

[0276] Compound BX can be prepared by the methods described in the examples below. Furthermore, the compound BX obtained by the reaction can be purified to the desired high purity monomer using known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or combinations thereof.

[0277] (Specific examples of compound BX)

[0278] The following are specific examples of compound BX. However, compound BX is not limited to the following compounds.

[0279]

[0280] (Content of compound B, etc.)

[0281] The raw material composition in this embodiment includes compound (A) and one or more compounds B.

[0282] In this embodiment, from the viewpoint of balancing the effect on stability over time and lithographic performance such as sensitivity, resolution and roughness, the total amount of compound B (the total amount of the compound shown in formula (2), the compound shown in formula (3) and the compound shown in formula (X)) relative to the total amount of the composition is preferably 1 ppm to 100,000 ppm by mass, more preferably 10 ppm to 50,000 ppm by mass, and particularly preferably 20 ppm to 10,000 ppm by mass.

[0283] The raw material composition is not particularly limited, but it preferably contains two or more compounds B. If two or more compounds B are included, there is a tendency for the etching defects during solid film exposure to be reduced, as described above. The reason for the reduction in etching defects is not yet clear, but it is thought to be, for example, that the compatibility of compound B in the composition is improved, resulting in a reduction of fine defects during film formation.

[0284] When two or more compounds B are used in combination, the amount of each compound B is not limited. However, if there is a compound (B) with a small amount of compound (B) (designated as compound B'), from the viewpoint of improving the etching defect effect, the amount of compound B' is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, in the total amount of compound B. In addition, if there is a compound B with the most compound (designated as compound B), from the viewpoint of improving sensitivity, the content of compound B', which has a lower iodine atom content in its molecule than compound B', is preferably 40% by mass or less in the total amount of compound B, more preferably 10% by mass or less, and most preferably 5% by mass or less.

[0285] In one approach, when the monomeric compound with a high iodine number in compound B is designated as H, the monomeric compound with a low iodine number as L, and the dimer compound as D, the following combinations can be exemplified.

[0286] H / L (mass ratio, the same below) = (99~99.9): (1~0.1).

[0287] H / D = (99~99.9): (1~0.1)

[0288] H / L / D=(98~99.9):(1~0.05):(1~0.05)

[0289] There are no restrictions on the method of mixing two or more compounds B. Two or more compounds B can be mixed, or they can be synthesized simultaneously in the form of a mixture during the synthesis of compound (B).

[0290] (Co)polymer

[0291] The (co)polymer of this embodiment contains structural units corresponding to compound A.

[0292] The (co)polymer of this embodiment can be obtained by (i) polymerization of compound A with other monomers, or (ii) polymerization of a raw material composition containing compound A and compound B with other monomers to obtain a (co)polymer containing structural units corresponding to compound A. By forming a polymer containing structural units corresponding to compound A, a (co)polymer containing one or more halogen elements can be formed. As a result, by using a film forming composition with the (co)polymer of this embodiment as a resin component, it is possible to achieve high sensitivity in photolithography processes, high resolution due to increased resin solubility contrast during development, and excellent roughness.

[0293] It should be noted that when the (co)polymer of this embodiment is synthesized by polymerization of a raw material composition containing compound A and compound B with other monomers, compound B may be contained in the main chain or side chain of the (co)polymer of this embodiment, or it may not be contained in the (co)polymer but only exist in its vicinity. As the (co)polymer of this embodiment, a polymer whose structure does not contain compound B is preferred.

[0294] Hereinafter, the composition comprising the (co)polymer of this embodiment and compound B (selected from at least one of the compounds shown in formula (2), formula (3), and formula (X)) will be referred to as a "resin composition".

[0295] The structure of the structural unit corresponding to compound A is not particularly limited. For example, when p is 1 in formula (1) (preferred formula (1A)), the (co)polymer of this embodiment contains the structural unit shown in formula (1C) below.

[0296]

[0297] In equation (1C), A1, A2, and R a R b R c X 1 、I、n 1 n 2 The meaning is the same as in equation (1). Additionally, the notation... Indicates the bonding site with the adjacent repeating unit.

[0298] The (co)polymer of this embodiment may contain structural units other than those corresponding to compound A, which are not particularly limited. For example, 2-ethyl-2-adamantyl methacrylate (EAMA), γ-butyrolactone methacrylate (GMA), and 4-vinylphenyl acetate (PHS-Ac) may be used. International Publication Nos. WO2016 / 125782, WO2015 / 115613, Japanese Patent Application Laid-Open No. 2015 / 117305, and WO20 The structural units described in Japanese Patent Application Publication No. 14 / 175275 and Japanese Patent Application Publication No. 2012 / 162498 may be used as commercially available products, such as γ-butyrolactone (meth)acrylate (trade names: GBLA, GBLMA), adamantyl alkyl monomers (MADA, MADMA, EtADA, EAMA(P)), monomers with phenolic hydroxyl groups (HQMA, HMAd, isobornyl methacrylate (IBOMA)), or compounds shown in formulas (C2) and (C3) below.

[0299]

[0300] (In formula (C2),)

[0301] R C11 Indicates hydrogen or methyl.

[0302] R C12 Indicates hydrogen or alkyl groups having 1 to 4 carbon atoms.

[0303] R C13 With R C13 The bonded carbon atoms together represent cycloalkyl or heterocycloalkyl groups with 4 to 20 carbon atoms.

[0304] point This indicates the bonding site with an adjacent repeating unit.

[0305] Preferred R C12 R represents an alkyl group having 1 to 3 carbon atoms or hydrogen atoms. C13 With R C13 The bonded carbon atoms together are cycloalkyl or heterocycloalkyl groups with 4 to 10 carbon atoms. R 13 Optionally, it may have substituents (e.g., oxo group).

[0306]

[0307] (In formula (C3),)

[0308] R C21 Indicates hydrogen or methyl.

[0309] R C22 and RC23 Each can independently represent an alkyl group having 1 to 4 carbon atoms.

[0310] R C24 Indicates alkyl groups having 1 to 4 carbon atoms or cycloalkyl groups having 5 to 20 carbon atoms.

[0311] R C22 ~R C24 Two or three of them can be selected together with the carbon atoms they are bonded to form an alicyclic structure with 3 to 20 carbon atoms.

[0312] point This indicates the bonding site with an adjacent repeating unit.

[0313] Preferred R C22 R represents an alkyl group having 1 to 3 carbon atoms. C24 It is a cycloalkyl group with 5 to 10 carbon atoms. Additionally, R... C22 ~R C24 The resulting alicyclic structure may also include multiple rings such as adamantyl alkyl groups. Furthermore, the alicyclic structure may optionally have substituents (e.g., hydroxyl, alkyl groups).

[0314] The monomeric raw material used as the repeating unit shown in formula (C3) above is not limited, and examples 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-dimethylnaphthalene, 2-ethyl-2-(meth)acryloyloxynorbornane, etc. Commercially available products can be used as these monomers.

[0315] [Method for manufacturing the (co)polymer of this embodiment]

[0316] Next, a method for manufacturing the (co)polymer using this embodiment will be described. The polymerization reaction is carried out simultaneously with the monomer, which will become a repeating unit, dissolved in a solvent and heated or cooled while a catalyst is added. The reaction conditions can be arbitrarily set according to the type of initiator, the initiation method (heat, light, etc.), temperature, pressure, concentration, solvent, additives, etc. The (co)polymer of this embodiment can be manufactured using known methods such as free radical polymerization using free radical generators such as azoisobutyronitrile (AIBN) or peroxides, or ionic polymerization using catalysts such as alkyllithium or Grignard reagents.

[0317] As solvents used in polymerization reactions, commercially available solvents can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, and halogenated solvents can be used appropriately within the limits that do not hinder the reaction. Multiple solvents can also be used in combination within the limits that do not hinder the above-mentioned reactions.

[0318] The (co)polymer obtained by polymerization can be purified by known methods. Specifically, ultrafiltration, crystallization, microfiltration, acid washing, washing with water with a conductivity of less than 10 mS / m, and extraction can be combined.

[0319] In the case where the (co)polymer of this embodiment contains other structural units, the content of the structural unit corresponding to compound A is preferably 1 to 99 mol% relative to the total amount of the (co)polymer, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%, from the viewpoint of sensitivity, resolution, roughness in photolithography and the time stability of the resin composition.

[0320] Resin Compositions

[0321] As described above, a resin composition can be prepared by resinifying the composition (raw material composition) of this embodiment, which includes compound A and compound B. That is, the resin composition of this embodiment is a composition comprising the (co)polymer of this embodiment and at least one compound (compound B) selected from the compounds shown in formula (2), formula (3), and formula (X). When the raw material composition of this embodiment is resinified, i.e., compound A is resinified in the presence of compound B, a (co)polymer containing structural units corresponding to compound A and in which compound B is present can be synthesized. This improves the sensitivity, resolution, roughness, and time-dependent stability of the resin composition in photolithography. The resinification of the raw material composition can be performed using the same method as the resinification of compound A.

[0322] Compositions for film formation

[0323] The film-forming composition of this embodiment comprises compound A, a raw material composition, and a (co)polymer or resin composition. The film-forming composition of this embodiment is useful in photolithography applications for semiconductor photolithography, and is particularly useful as a resist film-forming composition for semiconductor photolithography. Hereinafter, the film-forming composition of this embodiment will be described using photolithography applications as an example.

[0324] The (co)polymer and resin composition comprising both of the present invention and compound B exhibit a sensitizing effect on the photolithography composition containing the present invention under radiation irradiation. The reason for this is not limited, but it is believed to be due to the compound promoting the absorption of radiation. This effect is particularly pronounced under extreme ultraviolet (EUV) irradiation. The sensitizing effect can take many forms. When using a photosensitive layer prepared using the photolithography composition as a photoresist film, it can be confirmed, for example, as follows: 1) After exposure using a patternless surface exposure method, the film thickness is measured after a PEB process (a process involving heat treatment after exposure) and a development process (a process in which the exposed or unexposed areas are dissolved and removed using a developer) as needed. 2) The film thickness is measured by changing the exposure amount, and the exposure amount at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed at a low exposure amount, it can be considered that a sensitizing effect is present. Furthermore, in the method of pattern formation by exposure, 1) the exposure amount is changed to form a pattern, and the exposure amount at which the linewidth becomes a specified linewidth after exposure is defined as the sensitivity. 2) If sensitivity is confirmed at a lower exposure level, it can be considered to have an enhancing effect. Furthermore, this can be confirmed, particularly in extreme ultraviolet (EUV) pattern evaluation, by reducing defects such as pitting and bridging. These defects arise from fluctuations in optical exposure or exposure states that are substantially similar to defects due to low exposure. However, if the resist film has an enhancing effect, these fluctuations or defects are avoided through absorption promotion, thus reducing these defects. When using compounds A and B in a photolithography composition, compounds A and B can be used directly as components of the composition. Alternatively, it can be processed into a form containing a resin (substrate (A)) with compound A as a partial structure, additives (acid-generating agent (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc.), and used as a photolithography composition with these resins and additives as components.

[0325] The film-forming composition of this embodiment preferably contains, alone or together with compound B, a (co)polymer containing structural units corresponding to compound A. Depending on the requirements, it may also contain other components such as a substrate (A), solvent (S), acid-generating agent (C), crosslinking agent (G), and acid diffusion control agent (E). The components will be described below.

[0326] [Substrate (A)]

[0327] In this embodiment, "substrate (A)" refers to compounds other than compound A, compound B, and (copolymer) (including resins) used in this embodiment. It is a substrate used as a photoresist for gamma rays, i-rays, KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), and electron beam (EB) lithography (e.g., a photolithography substrate, a photoresist substrate). There are no particular limitations on any of these substrates, and they can all be used as substrate (A) in this embodiment. Examples of substrate (A) include phenolic resin, cresol resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cyclic olefin-maleic anhydride copolymer, cyclic olefin, vinyl ether-maleic anhydride copolymer, and inorganic photoresist materials containing metallic elements such as titanium, tin, hafnium, or zirconium, as well as their derivatives. From the viewpoint of the shape of the obtained resist pattern, preferred materials include phenolic resin, cresol resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, and inorganic resist materials containing metallic elements such as titanium, tin, hafnium, and zirconium, as well as their derivatives.

[0328] There are no particular limitations on the derivatives mentioned above; for example, derivatives formed by introducing dissociative groups or crosslinking groups can be included. The derivatives formed by introducing dissociative groups or crosslinking groups can exhibit dissociation and crosslinking reactions through the action of light, acids, etc.

[0329] "Dissociable groups" refer to characteristic groups that generate base-soluble functional groups or other functional groups that change solubility through cleavage. There are no particular limitations on base-soluble groups, and examples include phenolic hydroxyl groups, carboxyl groups, sulfonic acid groups, and hexafluoroisopropanol groups. Phenolic hydroxyl groups and carboxyl groups are preferred, with phenolic hydroxyl groups being particularly preferred.

[0330] "Crosslinking group" refers to a group that crosslinks in the presence or absence of a catalyst. There are no particular limitations on crosslinking groups, but examples include alkoxy groups with 1 to 20 carbon atoms, groups containing allyl groups, groups containing (meth)acryloyl groups, groups containing epoxy (meth)acryloyl groups, groups containing hydroxyl groups, groups containing urethane (meth)acryloyl groups, groups containing glycidyl groups, and groups containing vinylphenylmethyl groups.

[0331] [Solvent (S)]

[0332] In this embodiment, any known solvent may be used as long as it can at least dissolve the aforementioned iodine-containing (meth)acrylate compound and / or iodine-containing (meth)acrylate (co)polymer (B). Specific examples of solvents are not particularly limited, but can include 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; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-pentyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, and n-hexyl acetate; and methyl propionate, etc. Aliphatic carboxylic acid esters such as ethyl acetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, methyl 3-methoxybutylacetate, methyl 3-methoxy-3-methoxybutylacetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, and other esters; 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; lactones such as γ-lactone, etc., without particular limitation. The solvent used in this embodiment 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.

[0333] In this embodiment, the amount of solid components (the total amount of components other than solvent (S) (hereinafter the same)) and the amount of solvent are not particularly limited. Relative to the total mass of the amount of solid components and solvent, it is preferred that the solid components are 1 to 80% by mass and the solvent is 20 to 99% by mass, more preferably that the solid components are 1 to 50% by mass and the solvent is 50 to 99% by mass, even more preferably that the solid components are 2 to 40% by mass and the solvent is 60 to 98% by mass, and particularly preferably that the solid components are 2 to 10% by mass and the solvent is 90 to 98% by mass.

[0334] [Acid-producing agent (C)]

[0335] The composition of this embodiment preferably includes one or more acid-generating agents (C), which generate acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-rays, and ion beam. The acid-generating agent (C) is not particularly limited; for example, the acid-generating agent described in International Publication WO2013 / 024778 can be used. The acid-generating agent (C) can be used alone or in combination with two or more agents.

[0336] The amount of acid-generating agent (C) used is preferably 0.001 to 49% by mass of the total solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass. By using the acid-generating agent (C) within the above range, there is a tendency to obtain pattern profiles with high sensitivity and low edge roughness. In this embodiment, the method of acid generation is not particularly limited as long as acid is generated within the system. If an excimer laser is used instead of ultraviolet rays such as gamma rays or i-rays, finer processing can be performed. Furthermore, if electron beams, extreme ultraviolet rays, X-rays, or ion beams are used as high-energy rays, further fine processing can be performed.

[0337] [Alkali-producing agent (G)]

[0338] The case where the alkali-producing agent (G) is a photo-alkali-producing agent will be explained.

[0339] Photoalkali-producing agents refer to substances that produce alkali through exposure. However, there are no special restrictions on substances that do not show activity under normal conditions of room temperature and pressure but produce alkali (alkaline substances) when exposed to electromagnetic waves or heated as external stimuli.

[0340] In this embodiment, there are no particular limitations on the photo-alkali-generating agents that can be used. Well-known photo-alkali-generating agents can be used, such as carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, etc.

[0341] There are no particular limitations on the alkaline substances produced by photoalkali-producing agents. Examples include compounds with amino groups, especially monoamines, diamines, and other polyamines, or amidines.

[0342] From the perspective of sensitivity and resolution, the generated basic substance is preferably a compound with an amino group that has higher basicity (higher pKa value of the conjugate acid).

[0343] Examples of photo-alkali-generating agents include, for example, those with a cinnamamide structure disclosed in Japanese Patent Application Publication No. 2009-80452 and International Publication No. 2009 / 123122; those with a carbamate structure disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747; those with an oxime structure and a carbamoyl oxime structure disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581; and compounds described in Japanese Patent Application Publication No. 2010-243773. However, these are not limited to these examples, and the structures of known alkali-generating agents may also be used.

[0344] The photo-alkali-generating agent can be used alone or in combination of two or more. The preferred content of the photo-alkali-generating agent in the film-forming composition is the same as the preferred content of the aforementioned acid-generating agent in the film-forming composition.

[0345] [Acid diffusion control agent (E)]

[0346] In this embodiment, an acid diffusion control agent (E) can be incorporated into the composition. This acid diffusion control agent (E) controls the diffusion of acid generated from the acid-generating agent due to radiation irradiation into the resist film and prevents undesirable chemical reactions in unexposed areas. By using the acid diffusion control agent (E), the storage stability of the composition of this embodiment tends to be improved. Furthermore, by using the acid diffusion control agent (E), the resolution of the film formed using the composition of this embodiment can be improved, and the linewidth variation of the resist pattern caused by changes in the placement time before and after radiation irradiation can be suppressed, resulting in superior process stability. The acid diffusion control agent (E) is not particularly limited; examples include radiation-decomposing basic compounds such as nitrogen-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0347] There are no particular limitations on the acid diffusion control agent (E), for example, the acid diffusion control agent described in International Publication No. WO2013 / 024778 can be used. The acid diffusion control agent (E) can be used alone or in combination with two or more.

[0348] The mixing amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total solid components, 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. When the mixing amount of the acid diffusion control agent (E) is within the aforementioned range, there is a tendency to prevent the reduction in resolution, the deterioration of pattern shape, dimensional fidelity, etc. Furthermore, even if the placement time from electron beam irradiation to post-radiation heating is prolonged, the shape deterioration of the upper layer of the pattern can be suppressed. In addition, when the mixing amount is 10% by mass or less, there is a tendency to prevent the reduction in sensitivity, the developability of unexposed areas, etc. In addition, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the linewidth variation of the resist pattern caused by the variation of the placement time before and after radiation can be suppressed, resulting in excellent process stability.

[0349] [Other ingredients (F)]

[0350] In the composition of this embodiment, as other components (F), one or more crosslinking agents, solubility promoters, solubility control agents, sensitizers, surfactants, and various additives such as organic carboxylic acids or oxyacids of phosphorus or their derivatives may be added as needed.

[0351] (Cross-linking agent)

[0352] In this embodiment, the composition may contain more than one crosslinking agent. A crosslinking agent is a compound capable of crosslinking at least one of the substrate (A) or an iodine-containing (meth)acrylate compound and / or an iodine-containing (meth)acrylate (co)polymer (B). Preferably, an acid crosslinking agent is one capable of intramolecularly or intermolecularly crosslinking the substrate (A) in the presence of an acid generated by an acid-producing agent (C). Examples of such acid crosslinking agents include compounds having one or more groups capable of crosslinking the substrate (A) (hereinafter referred to as "crosslinking groups").

[0353] Examples of crosslinking groups include (i) hydroxyl (alkyl group with 1 to 6 carbon atoms), alkoxy (alkyl group with 1 to 6 carbon atoms), acetoxy (alkyl group with 1 to 6 carbon atoms), and other hydroxyalkyl groups or groups derived therefrom; (ii) carbonyl groups or groups derived therefrom, such as formyl group and carboxyl group (alkyl group with 1 to 6 carbon atoms); (iii) nitrogen-containing groups such as dimethylaminomethyl, diethylaminomethyl, dihydroxymethylaminomethyl, dihydroxyethylaminomethyl, and morpholinemethyl; (iv) glycidyl ether group, glycidyl ester group, glycidyl amino group, and other groups containing glycidyl group; (v) aromatic groups such as benzyloxymethyl and benzoyloxymethyl derived from aromatic groups such as allyloxy (alkyl group with 1 to 6 carbon atoms) and aralkyloxy (alkyl group with 1 to 6 carbon atoms); and (vi) groups containing polymerizable multiple bonds such as vinyl and isopropenyl groups. The crosslinking groups used as crosslinking agents in this embodiment are preferably hydroxyalkyl and alkoxyalkyl groups, and particularly preferably alkoxymethyl groups.

[0354] There are no particular limitations on the crosslinking agent having the aforementioned crosslinking groups; for example, the acid crosslinking agent described in International Publication No. WO2013 / 024778 can be used. The crosslinking agent can be used alone or in combination with two or more agents.

[0355] In this embodiment, the amount of crosslinking agent is preferably 50% or less of the total mass of the solid components, more preferably 40% or less, even more preferably 30% or less, and particularly preferably 20% or less.

[0356] (Solubility accelerator)

[0357] A solubility accelerator is a component that increases the solubility of a solid component in the developer when the solubility is too low, thereby appropriately increasing the dissolution rate of the compound during development. Low molecular weight solubility accelerators are preferred, for example, low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. These solubility accelerators can be used alone or in combination of two or more.

[0358] The amount of the dissolution promoter is adjusted appropriately according to the type of solid component used, preferably 0 to 49% by mass of the total mass of the solid component, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0359] (Dissolver control agent)

[0360] A solubility control agent is a component that controls the solubility of a solid component in the developer, thereby appropriately reducing the dissolution rate during development when the solubility of the solid component in the developer is too high. Preferably, such a solubility control agent does not undergo chemical changes during processes such as resist coating firing, radiation irradiation, and development.

[0361] There are no particular limitations on the use of solubility control agents. Examples include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These solubility control agents can be used alone or in combination.

[0362] The amount of the dissolving control agent is adjusted appropriately according to the type of compound used, preferably 0 to 49% of the total mass of the solid components, more preferably 0 to 5% of the total mass, further preferably 0 to 1% of the total mass, and particularly preferably 0% of the total mass.

[0363] (Sensitizer)

[0364] Sensitizers are components that absorb the energy of irradiated radiation and transfer that energy to the acid-generating agent (C), thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, diacetyl groups, pyrene groups, phenothiazines, and fluorene groups, among others, without particular limitation. These sensitizers can be used alone or in combination.

[0365] The amount of sensitizer mixed is adjusted appropriately according to the type of compound used, preferably 0 to 49% by mass of the total mass of solid components, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0366] (surfactant)

[0367] Surfactants are components that improve the coatability, streak characteristics, and developability of the resist in the compositions of this embodiment. Surfactants can be any type of anionic, cationic, nonionic, or amphoteric surfactant. Nonionic surfactants are preferred. Nonionic surfactants have good affinity with the solvents used in the manufacture of the compositions of this embodiment, further improving the effects of the compositions. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyethylene glycol, etc., without particular limitation. Commercially available products of these surfactants, listed below by product name, include Eftop (manufactured by JEMCO), MEGAFACE (manufactured by Dai Nippon Ink & Chemical Co., Ltd.), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard, SURFLON (manufactured by Asahi Glass Co., Ltd.), Pepper (manufactured by Toho Chemical Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and POLYFLOW (manufactured by Kyoei-sha Oil & Fat Chemical Co., Ltd.).

[0368] The amount of surfactant is adjusted appropriately according to the type of solid component used, preferably 0 to 49% of the total mass of the solid component, more preferably 0 to 5% of the total mass, further preferably 0 to 1% of the total mass, and particularly preferably 0% of the total mass.

[0369] (Organic carboxylic acids or oxyacids of phosphorus or their derivatives)

[0370] To prevent sensitivity degradation or improve resist pattern shape and stability, the resist can be further formulated as an oxyacid containing organic carboxylic acids or phosphorus, or its derivatives. It should be noted that the organic carboxylic acids or phosphorus oxyacids, or their derivatives, can be used in combination with an acid diffusion control agent or alone. Examples of preferred organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Examples of preferred phosphorus oxyacids or their derivatives include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acids or their ester derivatives; phosphonic acids, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonic acids or their ester derivatives; hypophosphonic acid, phenylhydantoin, and other hypophosphonic acids and their ester derivatives, with phosphonic acid being particularly preferred.

[0371] Organic carboxylic acids or oxyacids of phosphorus or their derivatives may be used alone or in combination with two or more. The amount of organic carboxylic acids or oxyacids of phosphorus or their derivatives may be adjusted appropriately according to the type of compound used, preferably 0 to 49% by mass of the total solid content, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0372] [Other Additives]

[0373] Furthermore, the composition of this embodiment can be mixed with one or more additives other than the aforementioned components as needed. Examples of such additives include dyes, pigments, and adhesive additives. For example, mixing in dyes or pigments can make the latent image of the exposed portion visible and mitigate the effect of halo during exposure, which is therefore preferred. Additionally, mixing in adhesive additives can improve adhesion to the substrate, which is also preferred. Furthermore, other additives include anti-halo agents, preservation stabilizers, defoamers, shape modifiers, etc., specifically 4-hydroxy-4'-methylchalcone, etc.

[0374] In the composition of this embodiment, the total amount of any component (F) can be set to 0 to 99% of the total mass of the solid components, preferably 0 to 49% of the total mass, more preferably 0 to 10% of the total mass, even more preferably 0 to 5% of the total mass, even more preferably 0 to 1% of the total mass, and particularly preferably 0% of the total mass.

[0375] The composition of this embodiment forms a resist pattern, and the composition solution is coated onto a substrate such as a silicon wafer, metal, plastic, glass, or ceramic using a suitable coating method such as a spin coater, dip coater, or roll coater, thereby forming a resist film. After preheating at a temperature of approximately 50°C to 200°C, the film is exposed through a predetermined mask pattern. The thickness of the coating is, for example, 0.1 to 20 µm, preferably approximately 0.3 to 2 µm. Exposure can utilize light of various wavelengths, such as ultraviolet light or X-rays. For example, as a light source, far-ultraviolet light such as an F2 excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm), extreme ultraviolet light (wavelength 13 nm), X-rays, or electron beams can be appropriately selected. Furthermore, exposure conditions such as exposure amount can be appropriately selected based on the formulation of the resin and / or compound, the types of additives, etc.

[0376] In this embodiment, to stably form a high-precision micro-pattern, it is preferable to perform a heat treatment at a temperature of 50-200°C for 30 seconds or more after exposure. In this case, when the temperature is below 50°C, the sensitivity deviation caused by the type of substrate may increase. Then, using an alkaline developer, development is typically performed at 10-50°C for 10-200 seconds, preferably at 20-25°C for 15-90 seconds, thereby forming the specified resist pattern.

[0377] As the aforementioned alkaline developer, for example, an alkaline aqueous solution is used, prepared by dissolving alkaline compounds such as alkali metal hydroxides, ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene into an aqueous solution with a concentration of 1 to 10% by weight, preferably 1 to 3% by weight. Furthermore, water-soluble organic solvents and surfactants may be appropriately added to the developer prepared from the aforementioned alkaline aqueous solution.

[0378] [Uses of compositions for film formation]

[0379] The film-forming composition of this embodiment is a film-forming composition comprising the aforementioned composition or resin composition, and is particularly suitable for film-forming in photolithography. Furthermore, the composition comprising the film-forming composition may, for example, be a photolithography film-forming composition suitable for semiconductor photolithography film formation. Additionally, the composition comprising the film-forming composition may, for example, be a resist film-forming composition suitable for resist film formation (i.e., a "resist composition"). Moreover, the film-forming composition can be used for upper layer film formation (i.e., "upper layer film-forming composition"), intermediate layer formation (i.e., "intermediate layer film-forming composition"), lower layer film formation (i.e., "lower layer film-forming composition"), etc. For the purpose of improving the patterning performance of the resist layer in the photolithography process, they can primarily or secondarily perform functions such as preventing reflection, preventing the diffusion of secondary electrons, and improving pattern quality based on chemical and physical effects, such as pattern collapse, defects, and pattern shape maintenance. The composition according to this embodiment can form a film with high sensitivity and impart a good resist pattern shape.

[0380] The compounds, (co)polymers, compositions, resin compositions, and film-forming compositions of this embodiment can also be used in the form of optical component forming compositions using photolithography. Besides being used in film or sheet form, optical components can also be used as plastic lenses (prism lenses, cylindrical lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed circuit boards, electroplating resists, interlayer insulating films for multilayer printed circuit boards, photosensitive waveguides, liquid crystal displays, organic electroluminescent (EL) displays, photoelectric semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitive solar cells, and organic thin-film transistors (TFTs). The compositions are particularly suitable for use as components in solid-state imaging elements requiring high refractive indices, namely, embedded films and planarization films on photodiodes, planarization films before and after color filters, microlenses, and planarization and conformal films on microlenses.

[0381] Example

[0382] The present invention will be further described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0383] [Determination Method]

[0384] The structure of the compounds was determined using a Bruker Avance 500III spectrometer under the following conditions. 1 H-NMR measurements were performed and confirmed.

[0385] Frequency: 500MHz

[0386] Solvent: CDCl3 or d6-DMSO

[0387] Internal label: TMS

[0388] Measurement temperature: 23℃

[0389] In addition, regarding 13 C-NMR measurements were performed using the same apparatus under the following conditions.

[0390] Frequency: 125MHz

[0391] Solvent: CDCl3 or d6-DMSO

[0392] Internal standard: Use solvent

[0393] Measurement temperature: 23℃

[0394] Synthesis of Compound A

[0395] [Synthesis example A1]

[0396] Compound (A1) was synthesized according to the following scheme.

[0397]

[0398] In a reaction vessel, 13.1 g of the tertiary alcohol (compound (A1-2): 2-(4-iodophenyl)propane-2-ol, 1 equivalent), 150 g of acetonitrile, and 9.1 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (1.2 equivalent) were added and dissolved. Under ice-cooled conditions until the internal temperature was below 5°C, 12.6 g of trifluoroacetic anhydride (1.2 equivalent) was added dropwise under a nitrogen stream and stirred for 30 minutes. Next, while maintaining the internal temperature below 5°C, 20.5 g of the hydroxystyrene (compound (A1-1): 2,6-diiodo-4-vinylphenol, 1.1 equivalent) was added dropwise and stirred for 60 minutes. Then, 0.7 g of copper chloride (0.1 equivalent) was added and stirred at 0°C for 2 hours. Finally, 100 mL of a saturated ammonium sulfate aqueous solution was added and stirred at 120 rpm for 30 minutes. Then, 300 mL of toluene was added, and the mixture was stirred at 120 rpm and allowed to stand. After standing, the aqueous phase was removed. The following treatment was performed twice: 100 mL of deion-exchanged water was added, and the mixture was stirred at 120 rpm for 10 minutes, allowed to stand, and then the aqueous phase was removed. The organic phase was then recovered and purified using a silica gel column to obtain 25.6 g of the target compound (A1).

[0399] 7.7(2H, Ph), 7.6(2H, Ph), 7.1(2H, Ph), 6.7(1H, =CH-), 5.8(1H, =CH2), 5.3(1H, =CH2), 1.6(6H, -CH3)

[0400] [Synthesis Examples A2 to A24]

[0401] In Synthesis Example A1, the compounds listed in the table below were used in place of the tertiary alcohol body (compound (A1-2)) and the hydroxystyrene body (compound (A1-1)) in the same molar amounts as those listed in the table below. Otherwise, the compounds corresponding to each synthesis example were synthesized in the same manner.

[0402] [Table 1]

[0403]

[0404] [Table 2]

[0405]

[0406] The compounds obtained in the above synthetic examples are shown below.

[0407]

[0408]

[0409]

[0410] [Synthesis example B1]

[0411] (Synthesis of vinyl ethers)

[0412] The "vinyl ether" is synthesized from the "alcohol" according to the following scheme.

[0413]

[0414] Prepare a 500 mL three-necked flask connected to a reflux tube and dry it. Next, add 37.6 g of the "alcohol" (compound (B1-1): 100 mmol), vinyl acetate (17.2 g, 2 equivalents), sodium carbonate (6.36 g, 60 mmol), 100 mL of dehydrated toluene, and IrCl(cod)2 (dichlorobis(1,5-cyclooctadiene)diiridium) (672 mg, 0.01 equivalents). Dissolve the precipitate under a nitrogen stream and stir at 100 °C and 120 rpm for 2 hours. Then, filter out the precipitate, add 100 mL of diethyl ether, stir at 120 rpm, and allow to stand to remove the diethyl ether phase. Recover the toluene phase, remove the solvent by vacuum distillation, and purify using a silica gel column to obtain 24.1 g of the "vinyl ether" (compound (B1-2)) as the target analyte.

[0415] (Acetalization process: Synthesis of the target compound)

[0416] Compound (B1) was synthesized according to the following scheme.

[0417]

[0418] Prepare a 500 mL three-necked flask connected to a reflux tube. Next, under a nitrogen stream, add 168 mL of dehydrated tetrahydrofuran (THF) and dissolve 37.2 g of the "hydroxystyrene body" (compound (B1-3)) at 120 rpm with a meniscus-shaped stirrer. Then, while stirring in an ice bath, add 8 g of pyridine-p-toluenesulfonic acid (PPTS) over 30 minutes, and continue stirring for another 60 minutes. Add the synthesized "vinyl ether body" (compound (B1-2): 48.2 g, 1.2 equivalents) dropwise to the stirred reaction solution over 60 minutes, and continue stirring at 35°C for another 60 minutes. Then, add 720 mL of pure water in an ice bath, stir for 60 minutes, and recover the organic phase. Add 200 mL of ethyl acetate and 500 mL of pure water to the recovered organic phase, stir, and recover the organic phase. Concentrate under reduced pressure to obtain 49.4 g of the alcohol body (B1) as the target compound. The yield was 80%.

[0419] [Synthetic Examples B2~B48]

[0420] In Synthesis Example B1, the compounds listed in the table below were used in place of the alcohol (compound (B1-1)) and the hydroxystyrene (compound (B1-3)) in an equimolar amount relative to Synthesis Example B1. Otherwise, the compounds corresponding to each synthesis example were synthesized in the same manner.

[0421] [Table 3]

[0422]

[0423] [Table 4]

[0424]

[0425] [Table 5]

[0426]

[0427] It should be noted that a portion of the alcohol used above is synthesized through the following process.

[0428] (Synthesis of alcohol (compound Bx-1): reduction reaction)

[0429]

[0430] Using a 1L three-necked flask, 24.6g of iodoacetophenone, 130mL of methanol, and 130mL of toluene were added. The mixture was stirred at 120rpm for 30 minutes with a stirrer blade until dissolved. NaBH4 (sodium borohydride, 1.3g, 0.35 equivalent) was added under a nitrogen atmosphere at an internal temperature of 0°C, and the mixture was stirred for 4 hours. Then, 100mL of saturated ammonium chloride aqueous solution was added, followed by 200mL of ethyl acetate. The mixture was stirred at 120rpm for 30 minutes, allowed to stand, and the aqueous phase was removed. This process was repeated three times: 100mL of deionized water was added, the mixture was stirred at 120rpm for 30 minutes, and the aqueous phase was removed after standing. The resulting organic phase was concentrated by vacuum distillation to obtain 23.3g of an alcohol (represented as "alcohol" in the table above, compound (Bx-1)).

[0431] (Synthesis of tertiary alcohols (compound (By-1)))

[0432] -Iodination process: Synthesis of compound (3IADCA)-

[0433]

[0434] Using a 1000mL three-necked flask equipped with a reflux duct, 25g of hydroxyadamantane carboxylic acid and 296g of 55% iodic acid were added. The internal temperature was raised to 60°C under a nitrogen flow, and the mixture was stirred at 120rpm for 6 hours using a meniscus-shaped stirrer. After cooling to room temperature, 319g of a 20% sodium sulfite aqueous solution was slowly added under ice-cooling conditions, and the mixture was stirred for 1 hour. After recovering the precipitate by filtration, 350g of toluene was added, and the mixture was heated to an internal temperature of 50°C to dissolve it. The following treatment was then performed three times: 180g of deionized water was added, and the mixture was stirred at 120rpm for 30 minutes, followed by standing to remove the aqueous phase. After concentration under reduced pressure at 50°C, 150mL of hexane was added, and the mixture was dispersed at 25°C. 34.3g of the iodide (compound (3IADCA)) precipitated as a result was recovered.

[0435] -Esterification process: Synthesis of compound (3IADCAM)-

[0436]

[0437] Using a 1000 mL three-necked flask equipped with a reflux duct, 29 g of the synthesized iodide (compound (3IADCA)), 290 mL of toluene, and 100 mg of DMF were added and dissolved by stirring with a meniscus-shaped stirrer. After cooling the internal temperature to 5 °C with ice, 22.5 g of thionyl chloride (2 equivalents) was added dropwise over 15 minutes with stirring. The internal temperature was then raised to 25 °C and stirred for 2 hours. After cooling the internal temperature to 10 °C, 30.2 g of methanol (10 equivalents) was added dropwise over 7 minutes. The internal temperature was then raised to 63 °C and stirred for 2 hours. After cooling to 25 °C, 300 mL of deionized water was added, followed by 150 mL of toluene. The mixture was stirred at 120 rpm for 30 minutes, then allowed to stand and the aqueous phase was removed. Next, the following steps were performed twice: 300 mL of ion-exchanged water was added, stirred at 120 rpm for 30 minutes, and then allowed to stand to remove the aqueous phase. Then, 150 mL of 5% sodium bicarbonate solution was added, stirred at 120 rpm for 30 minutes, and allowed to stand to remove the aqueous phase. After recovering the organic phase, 20 g of silica gel was added, stirred at 30 rpm for 40 minutes, and the filtrate was recovered by filtration. The silica gel was then washed with 50 mL of toluene, and the washing solution was recovered. The recovered organic phase was concentrated under reduced pressure to obtain 30 g of the target compound (ester body: compound (3IADCAM)).

[0438] -Synthesis based on methylated tertiary alcohol (compound (By-1))-

[0439]

[0440] Prepare a 1L three-necked flask and add 32.0g of the synthesized ester (compound (3IADCAM)) and 320mL of dehydrated THF. Under a nitrogen atmosphere and with the internal temperature at 0°C, while stirring at 120rpm using a meniscus-shaped stirrer, add 120mL of methyl magnesium bromide (1.0mol / L; THF solution) (1.2 equivalents) dropwise to maintain an internal temperature below 5°C, and continue stirring for 60 minutes. Next, add 100mL of saturated ammonium chloride aqueous solution and stir at 120rpm for 10 minutes, then add 300mL of ethyl acetate and stir at 120rpm for 10 minutes to remove the aqueous phase. Repeat the following operation twice: add 100mL of ion-exchanged water, stir at 120rpm, and remove the aqueous phase. Concentrate the recovered organic phase by vacuum distillation to obtain 30.4g of the tertiary alcohol (compound (By-1) in the table above, referred to as "alcohol"), which is the target compound.

[0441] The compounds obtained in the above synthetic examples are shown below.

[0442]

[0443]

[0444]

[0445]

[0446]

[0447]

[0448]

[0449] Synthesis of Resins Using Compound A

[0450] [Example of Resin Synthesis MA1: Synthesis of Polymer (MA1)]

[0451] 4.4 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 (PHS-Ac) 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, washed with 20 mL of methanol, and dried under reduced pressure to obtain 7.5 g of white powder.

[0452] The resulting white powder was dissolved in 50 mL of tetrahydrofuran. While stirring at 120 rpm with a stirring blade, 40 mL of 1M sodium hydroxide aqueous solution was slowly 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 continued. 40 mL of 1M ammonium chloride aqueous solution was slowly added and stirred for 30 minutes. Then, after two extractions with 60 mL of ethyl acetate, the resulting organic phase was concentrated by vacuum distillation. 20 mL of ethyl acetate was added to the concentrate, followed by crystallization with 100 mL of hexane. The concentrate was recovered by filtration, washed with hexane, and dried under vacuum to obtain 6.8 g of a white solid, yielding the polymer (MA1) shown below.

[0453] The polymer (MA1) has a weight-average molecular weight (Mw) of 11318 and a dispersity (Mw / Mn) of 1.89. Additionally, measurements were performed... 13 According to the C-NMR results, the composition ratio (molar ratio) in the following formula (MA1) is a:b:c:d = 30:30:10:30. It should be noted that the following formula (MA1) is simplified to represent the ratio of each structural unit, but the arrangement order of each structural unit is random, and it is not a block copolymer in which each structural unit forms its own independent block.

[0454]

[0455] It should be noted that the polystyrene monomers (compound (A1)) are directed to the carbon at the root of the benzene ring, while the methacrylate monomers (2-methyl-2-methacrylate adamantane ester, γ-butyrolactone methacrylate and hydroxyadamantane methacrylate) are directed to the carbonyl carbon of the ester bond. The molar ratio is determined based on their respective integral ratios.

[0456] [Examples of other resin synthesis]

[0457] In the following resin synthesis example MA1, compound (A1) was replaced with equimolar amounts of the compounds listed in the table above, and the polymers of each resin synthesis example were synthesized in the same manner. The following table shows the types and ratios (composition ratios) of each monomer in the polymers obtained in each resin synthesis example, the weight average molecular weight (molecular weight) of the obtained copolymers, and the dispersity.

[0458] [Comparative Synthesis Example 1]

[0459] In resin synthesis example MA1, an equimolar amount of EAMA was used to replace compound (A1). Otherwise, the same procedure as in resin synthesis example MA1 was followed to obtain the comparative polymer (MR1). This resin has a molecular weight (Mw) of 12300 and a dispersion (Mw / Mn) of 2.10. It should be noted that in the following formulas, "60", "10", and "30" represent the molar ratio of each structural unit. The formulas are simplified to represent the ratio of each structural unit, but this resin is not a block copolymer where each structural unit forms its own independent block.

[0460]

[0461] [Table 6]

[0462]

[0463] [Table 7]

[0464]

[0465] [Table 8]

[0466]

[0467] Preparation of Raw Material Compositions

[0468] <Synthesis of Compound B>

[0469] [Synthesis example BP1]

[0470] Synthesis of compound (BP1)

[0471] The compound (BP1) shown in the following formula (BP1) was synthesized by the method described below.

[0472]

[0473] 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-oxy radical, and 60 mL of DMSO (dimethyl sulfoxide) were added to the reactor and stirring was initiated. Next, using a Dean-Stark reactor and condenser, the conditions were adjusted to reflux at 120 °C under reduced pressure, and air was introduced into the reaction mixture at a flow rate of 1 mL / min. It should be noted that any water recovered in the Dean-Stark reactor was appropriately discharged from the system. The reactor was then immersed in a 90 °C water bath with continued stirring for 30 hours. Next, the reactor was immersed in a 25 °C water bath to cool the reaction mixture. Then, 500 g of a 0.1% (w / w) aqueous solution of sodium bisulfite was slowly added to the reaction mixture while vigorously stirring and mixing. Next, the precipitate was filtered and pressed using a vacuum filter, and washed with 200 mL of 33.3% (v / v) methanol aqueous solution. The precipitate was purified by column chromatography to separate only the major components. The solvent was removed by evaporation and distillation, and the resulting solid was dried under vacuum at 40 °C to obtain 8.1 g of a white solid. The yield was 26%.

[0474] Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 743.9, and confirmed the presence of compound (BP1) as shown in formula (BP1).

[0475] In addition, the above-mentioned measurement conditions were used for the following tests. 1 H-NMR determination revealed the following peaks, confirming the chemical structure of compound (BP1).

[0476] δ (ppm) (d6-DMSO): 9.6 (2H, OH), 7.5 (2H, Ph), 7.8 (2H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH3), 6.4~6.7 (2H, -CH=CH-)

[0477] [Synthesis example BP2~BP8]

[0478] Compared to Synthetic Example BP1, the starting material used was changed to 1-(4-hydroxy-3,5-diiodophenyl)ethanol, and equimolar amounts of the compounds listed in the table below were used. Otherwise, the compounds corresponding to each synthetic example were synthesized in the same manner.

[0479] [Table 9]

[0480]

[0481]

[0482] [Synthesis example BP1-Pro1]

[0483] Synthesis of compound (BP1-Pro1)

[0484] Using the compound (BP1) instead of "hydroxystyrene" (compound (B1-3)), the following compounds (BP1-Pro1) were synthesized in the same manner as in synthesis example B1.

[0485]

[0486] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1547, confirming the presence of the aforementioned compound (BP1-Pro1).

[0487] [Synthesis example BP3-Pro1]

[0488] The synthesis was performed in the same manner as in Synthesis Example BP1-Pro1, except that the starting material was changed to compound BP1 and an equimolar amount of the aforementioned compound BP3 was used.

[0489]

[0490] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1356, confirming the presence of the aforementioned compound (BP3-Pro1).

[0491] [Synthesis example BP6-Pro1]

[0492] Compared to the synthetic example BP6-Pro1, the starting material used was changed to compound BP1, and an equimolar amount of the aforementioned compound BP6 was used. Otherwise, the synthesis was carried out in the same manner.

[0493]

[0494] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1384, confirming the presence of the aforementioned compound (BP6-Pro1).

[0495] [Synthesis example BP1-Pro2]

[0496] Synthesis of compound (BP1-Pro2)

[0497] Using the compound (BP1) instead of "hydroxystyrene" (compound (B1-3)), the following compound (BP1-Pro2) was synthesized in the same manner as in synthesis example B5.

[0498]

[0499] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1604, confirming the presence of the aforementioned compound (BP1-Pro2).

[0500] [Synthesis example BP3-Pro2]

[0501] Synthesis of compound (BP3-Pro2)

[0502] Using the compound (BP3) instead of the "hydroxystyrene" (compound (B1-3)), the following compound (BP3-Pro2) was synthesized in the same manner as in synthesis example B5.

[0503]

[0504] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1412, confirming the presence of the aforementioned compound (BP3-Pro2).

[0505] [Synthesis example BP6-Pro2]

[0506] Synthesis of compound (BP6-Pro2)

[0507] Using the compound (BP6) instead of the "hydroxystyrene" (compound (B1-3)), the following compound (BP6-Pro2) was synthesized in the same manner as in synthesis example B5.

[0508]

[0509] Analysis using liquid chromatography-mass spectrometry (LC-MS) confirmed the molecular weight to be 1440, confirming the presence of the aforementioned compound (BP6-Pro2).

[0510] <Synthetic Example Group D>

[0511] [Synthetic Example D2]

[0512] (Synthesis of compound (D2))

[0513] -Iodination process: Synthesis of DML1D bodies-

[0514]

[0515] Using a 100L stainless steel reaction vessel connected to a reflux pipe, 700g of 4-hydroxybenzaldehyde and 4900ml of methanol were added. The mixture was stirred at 220rpm for 1 hour under a nitrogen stream until dissolved. The reaction vessel was ice-cooled. 757g of sodium hydroxide was dissolved in 1260mL of pure water. The synthesized sodium hydroxide aqueous solution was slowly added to the reaction vessel, followed by the slow addition of 3200g 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 hot water bath. Then, 21L of 6M hydrochloric acid aqueous solution was added dropwise at 120rpm for 1 hour under ice-cooling, followed by stirring for 30 minutes. Next, 2.3L of 20% sodium sulfite aqueous solution was added while stirring, followed by 3.5L of pure water. The precipitate was filtered and recovered. The obtained solid was purified by silica gel column chromatography, yielding 840g of DML1D in 30% yield.

[0516] -Protective group introduction process: Synthesis of the protectant DML1P-

[0517]

[0518] Using a 100L glass-lined reaction vessel connected to a reflux pipe, 840g of DML1D and 1680mL of dehydrated dimethylformamide (DMF) were added under a nitrogen flow and in an ice bath, and stirred until dissolved. Next, 380g of diisopropylethylamine was added dropwise over 30 minutes with stirring in an ice bath, followed by further stirring for 60 minutes. Then, 255g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise over 60 minutes with stirring in an ice bath, followed by further stirring for 30 minutes. Finally, 7.2L of pure water was added under ice bath and stirred for 60 minutes, followed by filtration to recover the precipitate. The recovered solid was suspended in 5.8L of methanol under ice bath and stirred for 30 minutes, followed by filtration to obtain 996g of a white solid as the protected form of the target compound, DML1P. The yield was 96%.

[0519] -Reduction process: Synthesis of compound (D2)-

[0520]

[0521] Using a 20L separable flask, after filling with 5L of ethanol in an ice bath, 996g of the synthesized protecting compound DML1P was slowly added to suspend it. Under a nitrogen stream and with stirring, 19g of sodium borohydride was added in 3g portions over 60 minutes. After stirring for 1 hour in an ice bath, 350g of a 5% (w / w) ammonium chloride aqueous solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was slowly added to 8L of pure water with stirring for 30 minutes. The precipitate that slowly formed during stirring was filtered off and further washed with 2L of pure water. The precipitate was dissolved in 4L of ethyl acetate and washed three times with 1.5L of a 10% (w / w) NaCl aqueous solution. After recovering the ethyl acetate solution, 80g of magnesium sulfate was added and the solution was suspended for 30 minutes. The filtrate was concentrated to approximately 50% (w / w) ± 5% and then crystallized in 9L of heptane. The filtered crystals were further washed with cooled heptane and then dried to obtain 701g of compound (D2) with a purity of 99.2% in a yield of 70%.

[0522] [Synthesis example D9]

[0523] (Synthesis of compound (D9))

[0524] 0. Reduction process: Synthesis of compound (D9)

[0525]

[0526] Using a 20L separable flask, after filling with 5L of ethanol in an ice bath, 996g of the protecting compound DML1P synthesized in Synthesis Example D2 was slowly added to suspend it. Under a nitrogen stream and with stirring, 19g of sodium borohydride was added in 3g portions over 60 minutes. After stirring for 1 hour in an ice bath, 350g of a 5% (w / w) ammonium chloride aqueous solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was slowly added to 8L of pure water with stirring for 30 minutes. The precipitate that slowly formed during stirring was filtered off and further washed with 2L of pure water. The precipitate was dissolved in 4L of ethyl acetate and washed three times with 1.5L of a 10% (w / w) NaCl aqueous solution. After recovering the ethyl acetate solution, 80g of magnesium sulfate was added and the mixture was suspended for 30 minutes. The filtrate was concentrated to a concentration of approximately 50% (w / w) ± 5% and then crystallized in 9L of heptane. The filtered crystals were further washed with cooled heptane and then dried to obtain 701g of compound (D9) with a purity of 99.2% in a yield of 70%.

[0527] [Synthesis example D1]

[0528] (Synthesis of compound (D1))

[0529] In contrast to the above-mentioned synthetic example D2, salicylaldehyde was used instead of 4-hydroxybenzaldehyde as a starting material in equal molar amounts, and compound (D1) was synthesized in the same manner as in synthetic example D9.

[0530]

[0531] [Synthesis example D8]

[0532] (Synthesis of compound (D8))

[0533] In contrast to the above synthetic example D9, salicylaldehyde was used instead of 4-hydroxybenzaldehyde as a starting material in equimolar amounts, and otherwise compound (D8) was synthesized in the same manner.

[0534]

[0535] [Synthesis example D5]

[0536] Synthesis of Toluene Adducts: Synthesis of Compound (D5)

[0537] A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 308 g of toluene was added to 21 g of 1,3,5-adamantanetriol, followed by 39.9 g of 55% sulfuric acid and 39.9 g of 55% hydrogen iodide aqueous solution, and the mixture was stirred. 26 g of distillate water was removed using a Dean-Stark tube at 105–110 °C, and the mixture was refluxed for 3 hours, then cooled to room temperature. 177.5 g of water was added, followed by 10 g of 10% sodium sulfite aqueous solution. The reaction mixture was then filtered, and the toluene solution and 31 g of crystals were filtered out. The toluene solution was then washed five times with 88 g of water to obtain 255 g of toluene solution. 341 g of ethyl acetate was added to the filtered 31 g of crystals and dissolved, followed by 85 g of water and 0.4 g of 10% sodium sulfite aqueous solution, and the mixture was washed again. The mixture was further washed six times with 85g of water to obtain 316g of ethyl acetate solution. 255g of toluene solution and 316g of the ethyl acetate solution containing the crystals were concentrated under reduced pressure. The precipitated crystals were filtered and dried under reduced pressure at 50°C to obtain 29.2g of white crystalline compound (D5).

[0538]

[0539] [Synthesis example D10]

[0540] Synthesis of Toluene Adducts: Synthesis of Compound (D10)

[0541] A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 308 g of toluene was added to 21 g of 1,3-adamantanediol, followed by 39.9 g of 55% sulfuric acid and 39.9 g of 55% hydrogen iodide aqueous solution, and the mixture was stirred. 26 g of distilled water was removed using a Dean-Stark tube at 105–110 °C, and the mixture was refluxed for 3 hours, then cooled to room temperature. 177.5 g of water was added, followed by 10 g of 10% sodium sulfite aqueous solution. The reaction mixture was then filtered, and the toluene solution and 31 g of crystals were filtered out. The toluene solution was then washed five times with 88 g of water to obtain 255 g of toluene solution. 341 g of ethyl acetate was added to the filtered 31 g of crystals and dissolved. Then, 85 g of water and 0.4 g of 10% sodium sulfite aqueous solution were added, and the mixture was washed again. The mixture was further washed six times with 85g of water to obtain 316g of ethyl acetate solution. 255g of toluene solution and 316g of the ethyl acetate solution containing the crystals were concentrated under reduced pressure. The precipitated crystals were filtered and dried under reduced pressure at 50°C to obtain 29.2g of white crystalline compound (D10).

[0542]

[0543] [Synthetic Example D16]

[0544] Synthesis of Toluene Adducts: Synthesis of Compound (D16)

[0545] A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 308 g of toluene was added to 19 g of 5-hydroxy-2-adamantanone, followed by 39.9 g of 55% sulfuric acid and 39.9 g of 55% hydrogen iodide aqueous solution, and the mixture was stirred. 26 g of distilled water was removed using a Dean-Stark tube at 105–110 °C, and the mixture was refluxed for 3 hours, then cooled to room temperature. 177.5 g of water was added, followed by 10 g of 10% sodium sulfite aqueous solution. The reaction mixture was then filtered, and the toluene solution and 31 g of crystals were filtered out. The toluene solution was then washed five times with 88 g of water to obtain 255 g of toluene solution. 341 g of ethyl acetate was added to the filtered 31 g of crystals and dissolved. Then, 85 g of water and 0.4 g of 10% sodium sulfite aqueous solution were added, and the mixture was washed again. The mixture was further washed six times with 85g of water to obtain 316g of ethyl acetate solution. 255g of toluene solution and 316g of the ethyl acetate solution containing the crystals were concentrated under reduced pressure. The precipitated crystals were filtered and dried under reduced pressure at 50°C to obtain 29.2g of white crystalline compound (D16).

[0546]

[0547] [Synthesis example D15]

[0548] Synthesis of Aldol Condensates: Synthesis of Compound (D15)

[0549] Prepare a 20L separable flask and add 4.8L of dehydrated THF and DBN (1,5-diazabicyclo[4.3.0]non-5-ene) (15.1g, 0.1 equivalent). Under a nitrogen flow, cool to an internal temperature of -15°C while stirring at 120 rpm for 1 hour using a meniscus-shaped stirrer. In another 3L flask, prepare a 4-iodoacetophenone-THF solution containing 1.2L of dehydrated THF and 300g of 4-iodoacetophenone. After adding the prepared 4-iodoacetophenone-THF solution dropwise to the 20L separable flask over 1.5 hours, raise the internal temperature to 40°C and stir for 4 hours.

[0550] After ice cooling to an internal temperature below 10°C, 300 g of saturated ammonium chloride aqueous solution was added. Next, 900 g of ion-exchanged water was added, followed by 3.0 kg of toluene. The mixture was stirred at 180 rpm for 15 minutes and allowed to stand before removing the aqueous phase. This process was repeated twice more: 1.2 kg of ion-exchanged water was added, stirred at 180 rpm for 15 minutes, and allowed to stand before the water tank was aspirated. The recovered organic phase was concentrated by vacuum distillation until the solvent components disappeared, and the peak containing the target analyte was separated by purification using a silica gel column. 160 g of the target analyte (D15) was obtained.

[0551] The obtained compound A3 (D15) was subjected to NMR analysis under the stated determination conditions, and the following peaks were observed, confirming that it has the chemical structure of the formula (D15).

[0552] δ (ppm) (CDCl3): 8.0 (2H, Ph), 7.6 (2H, Ph), 7.7 (2H, Ph), 7.1 (2H, Ph), 7.3 (1H, -CH=), 2.4 (3H, -CH3)

[0553]

[0554] [Preparation Example: PAZ1]

[0555] -Preparation of the raw material composition (PAZ1)-

[0556] In synthesis example A1, 50 g of compound (A1) (compound A) was dissolved in 500 g of ethyl acetate. Next, 0.05 g of compound (D15) (1000 ppm), which is compound B from synthesis example D15, was added to compound (A1), and the mixture was stirred for 30 minutes. Then, the solvent component (THF) was removed by vacuum concentration and vacuum drying to prepare the starting material composition (PAZ1).

[0557] [Preparation Examples: PAZ2~PBY54]

[0558] Compared to Preparation Example PAZ1, the raw materials used were changed to compounds A and B, and the corresponding compounds listed in the table below were used in the amounts listed in the table below. Otherwise, the raw material compositions corresponding to each preparation example were synthesized in the same manner.

[0559] [Table 10]

[0560]

[0561] [Table 11]

[0562]

[0563] [Table 12]

[0564]

[0565] [Table 13]

[0566]

[0567] [Table 14]

[0568]

[0569] [Table 15]

[0570]

[0571] [Table 16]

[0572]

[0573] Synthesis of Resins Using Raw Material Compositions

[0574] [Resin Synthesis Examples MAZ1~MBY54: Untreated]

[0575] In resin synthesis example MA1, the raw material composition listed in the table below in equimolar amounts was used instead of the compound (A1). Otherwise, the polymers corresponding to each resin synthesis example were synthesized in the same manner. The types and ratios (composition ratios) of each monomer in the polymers obtained in each resin synthesis example, the weight average molecular weight (molecular weight) of the obtained copolymers, and the dispersity are shown in the table below.

[0576] [Table 17]

[0577]

[0578] [Table 18]

[0579]

[0580] [Table 19]

[0581]

[0582] [Table 20]

[0583]

[0584] [Table 21]

[0585]

[0586] [Table 22]

[0587]

[0588] [Table 23]

[0589]

[0590] [Resin Synthesis Examples MASZ1~MBSY54: After Time Treatment]

[0591] In resin synthesis example MA1, the raw material composition described in the table below, which had undergone time treatment (stored in a light-proof bottle at 40°C for 3 months), was used in place of the compound (A1). Otherwise, the polymers corresponding to each resin synthesis example were synthesized in the same manner. The types and ratios (composition ratios) of each monomer in the polymers obtained in each resin synthesis example, the weight average molecular weight (molecular weight) of the obtained copolymers, and the dispersity are shown in the table below.

[0592] [Comparative Synthesis Example 2: Time-Related Treatment]

[0593] In Comparative Synthesis Example 1, a raw material composition in which 2-ethyl-2-adamantyl methacrylate (EAMA) g, γ-butyrolactone methacrylate (GMA), and 4-vinylphenyl acetate (PHS-Ac) were dissolved in cyclohexanone and subjected to aging treatment (stored at 40 °C for 3 months in a light-shielded bottle) was used. Except for this, a comparative polymer (PARZ1) was synthesized in the same manner.

[0594] [Table 24]

[0595]

[0596] [Table 25]

[0597]

[0598] [Table 26]

[0599]

[0600] [Table 27]

[0601]

[0602] [Table 28]

[0603]

[0604] [Table 29]

[0605]

[0606] [Table 30]

[0607]

[0608] 《Evaluation》

[0609] <EB Drawing (Evaluation of Sensitivity, Resolution, and Roughness)>

[0610] -Preparation of Film-Forming Composition-

[0611] Any one of the polymers obtained in each of the resin synthesis examples described in the following table (polymers containing compound A as a structural unit (resin synthesis examples MA1 to MB48), polymers containing compound A as a structural unit and compound B present nearby (resin compositions; resin synthesis examples MAZ1 to MBSY54), polymer of Comparative Synthesis Example 2 (PARZ1)): 5 parts by mass is mixed with triphenylsulfonium nonafluoromethanesulfonate (acid generator): 1 part by mass, tributylamine: 0.1 part by mass, and PGMEA: 94 parts by mass to prepare a film-forming composition. Further, the prepared film-forming composition is filtered in a clean room using a filter pipeline connected to a PTFE filter with a pore size of 15 nm (manufactured by Entegris) to obtain a filtered film-forming composition.

[0612] The obtained film-forming composition was coated on a silicon wafer and baked at 110 to 130 °C for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0613] Next, exposure was performed using an electron beam lithography apparatus (manufactured by ELIONIX; ELS-7500, 100 keV), baked (PEB) at 105 °C for 60 seconds, and immersed development was performed for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, rinsing treatment was performed with pure water, and after spinning at 1500 rpm for 30 seconds, a positive pattern was obtained.

[0614] The obtained pattern was observed by SEM (S4800, manufactured by Hitachi, Ltd.), and sensitivity, resolution, and roughness were evaluated. The results are shown in the following table.

[0615] Here, regarding the "sensitivity" evaluation, the lower limit value (mJ / cm 2 ) of the exposure dose capable of forming a pattern with a line width of 40 nm and a half pitch of 40 nm was determined as the EB sensitivity.

[0616] In addition, regarding the "resolution" evaluation, using a pattern layout condition PL in which the L (line) / S (space) ratio = 1 / 1 and the half pitch is decreased by 1 nm starting from 60 nm, and using an exposure dose condition D in which the exposure dose is decreased by 1 mJ / cm 2 starting from 60 mJ / cm 2 and decreasing by 1 mJ / cm, the pattern formation property was evaluated using a matrix of condition PL and condition D, and the line width at which the resolution became the minimum was determined.

[0617] In addition, regarding the "roughness" evaluation, for any 10 of the obtained line patterns, the standard deviation of the line width values when 30 points were obtained at an interval of 1 nm for each line was used as the roughness value for evaluation.

[0618] <EUV Sensitivity Evaluation>

[0619] The sensitivity of each film-forming composition prepared above to an EUV light source was evaluated using the following method.

[0620] First, the prepared film-forming compositions are coated onto different silicon wafers using a spin coater, and then heated at 105°C for 60 seconds using a heating plate to form a resist layer with a thickness of 100 nm.

[0621] Next, the entire wafer surface was subjected to extreme ultraviolet (EUV) exposure using an EUVES-7000 (manufactured by Lithotech Japan Co., Ltd.) at a concentration of 1 mJ / cm². 2 Starting with 1 mJ / cm 2 Increase the exposure to 80 mJ / cm 2 After maskless shot exposure, the wafer was baked at 105°C (PEB) for 60 seconds, followed by immersion development in a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, resulting in a wafer with 80 shot exposures. The film thickness of each exposed area was measured using an optical interferometer "VM3200" (manufactured by SCREEN Semiconductor Solutions Co., Ltd.). The film thickness versus exposure curve was obtained, and the exposure value with the largest slope of film thickness variation relative to exposure was calculated as the sensitivity value (mJ / cm²). 2 The value of α is used as an indicator of the EUV sensitivity of the resist. The results are shown in Tables 11-13.

[0622] <Evaluation of Exposure Defects in Solid Films>

[0623] The composition used in the EUV exposure sensitivity measurement was coated onto a 12-inch silicon wafer with a 100 nm thick oxide film on the outermost layer. The wafer was then baked at 105°C for 60 seconds to form a 100 nm thick photoresist layer. Next, the entire wafer surface was exposed using an extreme ultraviolet (EUV) exposure apparatus, “EUVES-7000” (manufactured by Lithotech Japan Co., Ltd.), with the same exposure amount as the EUV sensitivity value obtained in the EUV sensitivity evaluation described above. The wafer was then further baked (PEB) at 105°C for 90 seconds, followed by immersion development in a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, resulting in an exposed wafer with 80 shot exposures on the entire wafer surface.

[0624] The exposed wafers were etched using an etching apparatus called "Telius SCCM" (manufactured by TOKYO ELECTRON Corporation) with CH4 / CF4 / Ar gas until the oxide film thickness reached 40 nm. The wafers produced by etching were then evaluated for defects using a defect detection device called "Surfscan SP3" (manufactured by KLA Corporation). The number of tapered defects larger than 25 nm was determined as an indicator of etching defects according to the following evaluation criteria. The results are shown in the table below.

[0625] (Evaluation Criteria)

[0626] S: The number of conical defects is ≤ 5

[0627] A: 5 < Number of conical defects ≤ 20

[0628] B: 20 ​​< Number of conical defects ≤ 60

[0629] C: 60 < Number of conical defects ≤ 400

[0630] D: Number of 400 < Conical defects

[0631] [Table 31]

[0632]

[0633] [Table 32]

[0634]

[0635] [Table 33]

[0636]

[0637] [Table 34]

[0638]

[0639] [Table 35]

[0640]

[0641] [Table 36]

[0642]

[0643] [Table 37]

[0644]

[0645] [Table 38]

[0646]

[0647] [Table 39]

[0648]

[0649] [Table 40]

[0650]

[0651] [Table 41]

[0652]

[0653] [Table 42]

[0654]

[0655] [Table 43]

[0656]

[0657] [Table 44]

[0658]

[0659] [Table 45]

[0660]

[0661] [Table 46]

[0662]

[0663] [Table 47]

[0664]

[0665] The results above show that the film forming composition of the embodiments can form films with excellent sensitivity, resolution, roughness, EUV sensitivity, and solid film exposure defects.

[0666] The publication of Japanese Patent Application No. 2023-176017, filed on October 11, 2023, is incorporated herein by reference in its entirety.

[0667] In addition, all documents, patent applications and technical standards described in this specification are incorporated herein by reference in the same manner as those described herein.

Claims

1. A compound represented by the following formula (1), In equation (1), A1 represents an aromatic group with optional substituents. I represents an iodine atom. Q represents a dissociative group independently. A2 independently represents either an aliphatic or aromatic group with substituents. R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom. R b and R c Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom. X 1 Each can independently represent a single bond or a divalent linker. p represents an integer from 1 to 2. n 1 Represents integers from 1 to 6. n 2 Represents integers from 1 to 6. z represents an integer greater than or equal to 1.

2. The compound according to claim 1, wherein, A1 can be a benzene ring or a naphthalene ring with optional substituents.

3. The compound according to claim 1, wherein, The A2 is an optional aromatic group or a cyclic aliphatic group with substituents.

4. The compound according to claim 1, wherein, The dissociable groups are carbonate groups, acetal groups, ether groups, or alkoxy groups.

5. The compound according to claim 1, wherein, n 1 It is 1~2.

6. The compound according to claim 1, wherein, n 2 It is 1~2.

7. The compound according to claim 6, wherein, z is 1~2.

8. A composition comprising: the compound of claim 1, and at least one compound selected from the following formula (2), the following formula (3), and the following formula (X). In equation (2), A1 and R a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6, where, Multiple A1, R a R b R c X 1 n 11 Choose either the same or different. k represents an integer from 0 to 6. In equation (3), A2 and I have the same meaning as in equation (1), and n 22 Represents integers from 0 to 6, where multiple A2 and n 22 X 2 Choose either the same or different. X 2 Indicates a single bond or a divalent linker. m represents an integer from 0 to 6. In equation (X), A1, A2, Q, and R... a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6, where multiple A1, A2, Q, R... a R b R c X 1 n 11 Choose either the same or different. k represents an integer from 0 to 6.

9. The composition according to claim 8, wherein, At least one A1 in formula (2) is an optional benzene ring or naphthalene ring with substituents.

10. The composition according to claim 8, wherein, At least one A2 in formula (3) is an aromatic group or a cyclic aliphatic group that may have substituents.

11. The composition according to claim 8, wherein, At least one A1 in the formula (X) is an optional benzene ring or naphthalene ring with substituents.

12. The composition according to claim 8, wherein, The total amount of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (X) is 1 ppm by mass to 100,000 ppm by mass relative to the total amount of the composition.

13. A (co)polymer comprising a structural unit corresponding to the compound of claim 1.

14. A resin composition comprising: the (co)polymer of claim 13, and at least one compound selected from the compounds shown in formula (2), formula (3), and formula (X). In equation (2), A1 and R a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6, where, Multiple A1, R a R b R c X 1 n 11 Choose either the same or different. k represents an integer from 0 to 6. In equation (3), A2 and I have the same meaning as in equation (1), and n 22 Represents integers from 0 to 6, where multiple A2 and n 22 X 2 Choose either the same or different. X 2 Indicates a single bond or a divalent linker. m represents an integer from 0 to 6. In equation (X), A1, A2, Q, and R... a R b R c X 1 I has the same meaning as in equation (1), n 11 Represents integers from 0 to 6, where multiple A1, A2, Q, R... a R b R c X 1 n 11 Choose either the same or different. k represents an integer from 0 to 6.

15. A film-forming composition comprising the compound of any one of claims 1 to 7, the composition of any one of claims 8 to 12, the (co)polymer of claim 13, or the resin composition of claim 14.

16. The film-forming composition according to claim 15, wherein it is a film-forming composition for semiconductor lithography.

17. The film-forming composition according to claim 15, wherein it is a resist film-forming composition for semiconductor lithography.

18. A compound represented by the following formula (X), In formula (X), A1 represents an aromatic group with optional substituents. I represents an iodine atom. Q represents a dissociative group. A2 represents an optional aliphatic or aromatic group with substituents. R a Represents a hydrogen atom, methyl group, or halogen atom. R b and R c Represents a hydrogen atom, an aliphatic group, or a halogen atom. X 1 Indicates a single bond or a divalent linker. n 11 Represents integers from 0 to 6, where, Multiple A1, A2, Q, R a R b R c X 1 n 11 Choose either the same or different. k represents an integer from 0 to 6.

19. A compound represented by the following formula (W), In formula (W), A1 represents an aromatic group with optional substituents. I represents an iodine atom. R a Each can independently represent a hydrogen atom, a methyl group, or a halogen atom. R b and R c Each can independently represent a hydrogen atom, an aliphatic group, or a halogen atom. X 1 Each independently represents a divalent linker. p represents an integer from 1 to 2. n 1 Represents integers from 1 to 6. z represents an integer greater than or equal to 1.

20. The compound according to claim 19, wherein, In formula (W), X 1 The divalent linker shown is -R 3 -O-,R 3 This indicates an alkenyl group that may have optional substituents.

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